XVIth International Workshop on Quantum Systems in Chemistry and Physics 

List of Abstracts 
Unraveling nanoparticle properties using density functional theory 
Christine M. Aikens
Kansas State University, Manhattan, KS 66506, USA 
Theoretical investigations of monolayerprotected noble metal nanoparticles play an important role in determining the origins of the unique chemical and physical properties of these systems that lead to applications in photonics, sensing, catalysis, etc. In contrast to the strong plasmon resonance peak of larger nanoparticles, the optical absorption spectra of small (< 2 nm) nanoparticles display multiple peaks. Timedependent density functional theory (TDDFT) is employed to examine the spectrum of the Au_{25}(SR)_{18}^{} nanoparticle, and it is determined that delocalized orbitals in the 13atom nanoparticle core are primarily responsible for the excited state transitions. The ligand field arising from the surrounding goldthiolate oligomers is responsible for the splitting of the intraband transition.
In the past decade, several gold and silver nanoparticles have been determined to be chiral. Density functional theory calculations on the Au_{11}(BINAP)_{4}Cl_{2}^{+} system provide important information regarding ligand effects on core structure and the resulting circular dichroism spectra. The low energy peaks of Au_{11}L_{4}X_{2}^{+} arise mainly from transitions between delocalized metal superatom orbitals. Bidentate phosphine ligands have both a structural and electronic effect on the system. Whereas monodentate phosphine ligands lead to a C_{1} geometry, the lowest energy structure of Au_{11}L_{4}X_{2}^{+} has a chiral C_{2} structure. The chiral core of Au_{11}L_{4}X_{2}^{+} is not sufficient to explain the strong Cotton effects, and the intensity of the CD spectrum is increased by the presence of the bidentate phosphine ligands.
Using a combination of electronic structure calculations, XRD, and optical and chiroptical spectra, the “magic” Au_{38}(SR)_{24} nanocluster is shown to be chiral with D_{3} symmetry. Au_{38}(SR)_{24} is found to have an elongated, prolate structure; the electronic structure of this prolate “nanorod” is similar to that previously determined for silver nanorods. As for Au_{25}(SR)_{18}, delocalized superatomlike orbitals are responsible for its properties. 

FirstPrinciples Calculations of Hydrogen Impurities in Graphenes and Carbon Nanotubes 
Mohammad Shafiul Alam,^{1} Nyayu Siti Nurainun,^{1,2} Fahdzi Muttaqien,^{1,2} Agung Setiadi^{1,2} and Mineo Saito^{1,3}
^{1}Division of Mathematical and Physical Sciences, Graduate School of Natural Science and Technology,Kanazawa University, Kakuma Kanazawa 9201192, Japan
^{2}Department of Computational Science, Bandung Institute of Technology, Indonesia
^{3}Collaborative Research Center for Frontier Simulation Software for Industrial Science, Institute of Industrial Science, University of Tokyo, 461 Komaba, Meguroku Tokyo 1538505, Japan

Carbon Nanomaterials have attracted much attention since they are candidates for postsilicon materials. Since hydrogen is a common impurity in graphene [13] and carbon nanotubes (CNT), it is important to clarify how the hydrogen impurity affects the electronic structure of graphene and carbon nanotubes.
Now we are going to study monohydrogen in graphene, CNT (5,5) and CNT (10,0). We perform spinpolarized generalized gradient approximation by using firstprinciples calculations. In the most stable structure of monohydrogen, the hydrogen atom is bonded to one of the carbon atom in the graphene sheet [Fig. 1(a)] and also hydrogen atom is located on the outer side of CNT (5,5) [Fig. 1(b)] and CNT (10,0) [Fig. 1(c)]. The bond lengths between the hydrogen atom and the nearest neighbor carbon atom are 1.14 Ĺ, 1.12 Ĺ and 1.12 Ĺ for graphene, CNT (5,5) and CNT (10,0), respectively. These bond lengths are close to that in a CH_{4} molecule (1.09 Ĺ), which is typical for sp^{3} CH bond lengths. In these three cases [Fig. 1] the spin polarized states are found to be most stable and the magnetic moments are 1 μ_{B}.
References:
[1] M. Khazaei et al. CARBON 47, 3306 (2009).
[2] A. Ranjbar et al. Phys. Rev. B. 82, 165446 (2010).
[3] E. J. Duplock et al. Phys. Rev. Lett. 92, 2255021 (2004).

Figure 1. Spin densities of the monohydrogen in the graphene, CNT (5,5) and CNT (10,0).



Methylhydroxycarbene: Tunneling Control of a Chemical Reaction 
Wesley D. Allen
Department of Chemistry, University of Georgia, Athens, Georgia, USA 
Chemical reactivity is conventionally understood in broad terms of kinetic versus thermodynamic control, wherein the driving force is respectively the lowest activation barrier among the possible reaction paths or the lowest free energy of the final products. Here we expose quantum mechanical tunneling as a third driving force that can supersede traditional kinetic control and govern reactivity based on nonclassical penetration of the potential energy landscape intervening the reactants and products. These findings were afforded by the first experimental isolation and full spectroscopic and theoretical characterization of the elusive methylhydroxycarbene. Facile [1,2]hydrogen tunneling of methylhydroxycarbene to acetaldehyde occurs under a barrier of 28.0 kcal/mol with a halflife around 1 h, in preference to vinyl alcohol formation, which has a substantially lower barrier. 

Instanton calculations of rates and tunnelling splittings in water clusters and ice 
Jeremy O. Richardson^{1} and Stuart C. Althorpe^{1}
^{1} Department of Chemistry, University of Cambridge, UK 
This talk will explain how semiclassical instanton theory can be formulated very simply in terms of ringpolymers^{13}. The approach yields the dominant ‘instanton’ tunneling path through a potential barrier, which, together with quadratic fluctuations around this path, can be used to calculate reaction rates or tunnelingsplitting patterns. The approach is readily applied to multidimensional systems, including condensedphase systems with the application of periodic boundary conditions. We describe calculations of tunnelingsplitting patterns in water clusters (dimer, trimer and pentamer), and investigations of the rearrangement dynamics in ice.
1. J.O. Richardson and S.C. Althorpe, J. Chem. Phys. 131, 214106 (2009).
2. J.O. Richardson and S.C. Althorpe, J. Chem. Phys. 134, 054109 (2011).
3. S.C. Althorpe, J. Chem. Phys. 134, 114104 (2011). 

First principle theory for the material constants 
Marco Anelli, Dan Jonsson, Kenneth Ruud
Centre for Theoretical and Computational Chemistry, Department of
Chemistry, University of Tromsoe , 9037 Tromsoe , Norway 
The interactions between matter and electromagnetic fields are commonly analyzed using the constitutive relations,
which relate the applied electric and magnetic fields (E,B) to the response fields (D,H) through the material constants.
Therefore, material constants (also known as constitutive tensors) describe the response of the matter to the external fields.
In the case of a static perturbation, material constants are observable/measurable quantities, and they can been defined using multipole theory.
In contrast, when a dynamic field is considered, multipole theory leads to origindependent expressions for the material constants, and thus do not correspond to
physically acceptable observable quantities. There is therefore a need for originindependent definitions of the material constants.
Originindependent expressions of the material constants have been derived by Raab and de Lange applying a transformed multipole theory. They have also derived expressions for the material constants based on a covariant formulation of the constitutive relations. Both these theories provide expressions of the material constants
which are covariant, originindependent and preserve the spatial invariance of the wave equations. In the dynamic case, a unique definitions of the material constants still do not exist, and the possibility of deriving unique definitions for these quantities is still unresolved.
We will discuss our recent analysis of the problem, focusing on the pure electric and magnetic material constants, namely the electric permittivity and the inverse permeability. In particular, we will provide arguments in order to distinguish between the two possible definitions of the material constants proposed so far.
An important part of our analysis will be how to relate the material constants to wellknown measurable quantities. We propose that the absorption coefficient and the scattering amplitude, as defined in QED, can be expressed in terms of the electric permittivity, consistently with the definition provided by transformed multipole theory.


Generalized Quantum Similarity Index: a comparative density functional enclosing orbital short and longrange behaviors 
Juan Carlos Angulo
Departamento de Fisica Atomica, Molecular y Nuclear, and Instituto Carlos I de Fisica Teorica y Computacional, Universidad de Granada, E18071 Granada (Spain) 
A Generalized Quantum Similarity Index is defined, quantifying the similarity among density functions. The generalization includes, as new features (i) comparison among an arbitrary number of functions, (ii) its ability to modify the relative contribution of different regions within the domain, and (iii) the possibility of assigning different weights to each function according to its relevance on the comparative procedure. The similarity among atomic oneparticle densities in both conjugated spaces, and neutral–cation similarity in ionization processes are analyzed. The results are interpreted attending to shellfilling patterns, and also in terms of experimentally accessible quantities of relevance in ionization processes. 

Comments on the crosscoupling reaction 
Shigeyuki AONO
Kanazawa University, Kanazawa, Japan
Email address: aonosan2000@ybb.ne.jp 
Suzuki and Negishi have investigated the method of crosscoupling reaction which is a kind of catalytic reaction which effectively connect the carbon molecules.
Here we present a brief sketch of this reaction in the respect of chemical reactivity presented by Fukui and WoodwardHoffmann. Hückel treatment is made simple as possible: the energy levels of unit cell is put zero, the couplings are restricted adjacent and set unity (1). However the resultant bond order extends all over the molecule. In these simplification, the energy behavior looks as if the bond order ( q_{ij}). For butadiene, C_{4} chain, q_{14} is obtained negative which suggests the 14 sites are repulsive implying the ring closure between them never occurs. On the other hand q_{16} in the C_{6} chain is positive is positive, expecting The ring closure (making the benzene ring). Let us turn to the coupling reaction. For the simplest example, the system in which the dmetal connects two C_{2} molecule (ethylene). The dorbital is regarded as two porbitals, d_{xz} and d_{yz} (called 3 and 4th). Each ethylene connects the metal to form p_{z} bond and yield as if the molecule of six sites. The chain with six sites make chain, against the case of four members. We thus finished the beginning half of the reaction under consideration. The last half is to separate the metal and left the C_{4} chain, butadiene. Start from C_{6} ring, say benzene ring. We have now the ring, then the vertex is pointed 1. We evaluate the bond order q_{13} vanishing. We now find the 13 bond is nonbonding. If any perturbation happens, this bond is breaking and the metal being separates. Our purpose is completed. 

Nonadiabatic effects in the action of radiation on molecular systems 
MarieChristine BacchusMontabonel
Laboratoire de Spectrométrie Ionique et Moléculaire, CNRS et Université Lyon I, 43 Bd. Du 11 Novembre 1918, 69622 Villeurbanne Cedex, France, bacchus@lasim.univlyon1.fr 
Nonadiabatic interactions are the driving step in a number of mechanisms and special attention should be paid to the critical regions of the potential energy surfaces as avoided crossings or conical intersections where mixing and reorganization of electronic configurations may occur. These interactions may be observed in a large number of processes as phodissociation or charge transfer reactions. We have developed nonadiabatic methods based on wave packet propagation to calculate cross sections and rate constants in ionatom charge transfer collisions [1]. This approach may be particularly interesting for polyatomic systems of increasing complexity since it allows the possibility of separating the total configuration space into a subspace of n internal active coordinates which are quantum mechanically treated on ab initio potential energy surfaces, while inactive coordinates are treated in an approximate way, as in the constrained Hamiltonian methodology [2]. Such an approach has been applied on the very interesting example of the competitive dissociation of CCl and CBr bonds in bromoacetyl chloride BrCH2COCl photodissociation [3]. In such a process, nonadiabatic effects induce a trapping of the system before dissociation leading thus preferentially to CCl breaking, although the CBr bond should be weaker with regard to the relative height of energetic barriers along the reaction path.
In a different domain, action of ionizing radiations with biological tissues is known to induce severe damage to DNA. However, it has been shown [4] that important damage is not due to the radiation itself, but to secondary particles generated along the track after interaction of the radiation with the medium. We have studied the action of secondary ions with biomolecules; they may be involved either in direct process with biomolecules, or in indirect ones involving interaction of ions with the medium. The radiosensitivity of halouracils is analyzed in the direct collision with C4+ ions [5]. We present examples of indirect processes with the C2+ + OH and C2+ + CO collision systems which are driven by nonadiabatic interaction around avoided crossings between the different entry and exit channels [6].
References
1.N. Vaeck, M.C. BacchusMontabonel, E. Baloďtcha, M. DesouterLecomte, Phys. Rev. A 63, 042704 (2001).
2.D. Lauvergnat and A. Nauts, J. Chem. Phys. 116, 8560 (2002).
3.B. Lasorne, M.C. BacchusMontabonel, N. Vaeck, M. DesouterLecomte, J. Chem. Phys. 120, 1271 (2004).
4.B.D. Michael, P.D. O'Neill, Science 287, 1603 (2000).
5.M.C. BacchusMontabonel and Y.S. Tergiman, Chem. Phys. Lett (2011) (in press)
6.E. Rozsályi, E. Bene, G.J. Halász, Á. Vibók, M.C. BacchusMontabonel, Phys. Rev. A 81, 062711 (2010).


Electronic Absorption Spectra of the RgAr (Rg=Cs, Rb) Van der Waals Complexes 
J. Dhiflaoui^{a}, H. Berriche^{a,b} and M. C. Heaven^{c}
^{a}Laboratoire de Physique et Chimie des Interfaces, Département de Physique, Facultée des Sciences de Monastir, Avenue de l’Environnement, 5019 Monastir, Tunisie)
^{b}Physics Department, Faculty of Science, King Khalid University, P. O. Box 9004,
Abha, Saudi Arabia.
^{c}Chemistry Department, Emory University, Atlanta, USA
^{*}Email address: hamid.berriche@fsm.rnu.tn, hamidberriche@yahoo.fr 
The potential energy curves of the ground state and many excited states of the RbAr and CsAr van der Waals complexes have been determined using [Rb^{+}], [Cs^{+}] and [eAr] pseudopotentials with the inclusion of core polarization operators on both atoms. This has reduced the number of active electrons of the RgAr (Rg=Rb and Cs) system to only one valence electron, permitting the use of large basis sets for the Rb, Cs and Ar atoms. Potential energy curves of the ground state and many excited states have been calculated at the SCF level. The corecore interactions for Rg+Ar are included using the accurate CCSD potential of Hickling et al [Hickling, H.; Viehland, L.; Shepherd, D.; Soldan, P.; Lee, E.; Wright, T. Phys. Chem. Chem. Phys. 2004, 6, 4233]. Spectroscopic constants for the ground and excited states of RgAr are derived and compared with the available theoretical and experimental results. Furthermore, we have predicted the X^{2}Σ^{+}A^{2}Π_{1/2}, X^{2}Σ^{+}A^{2}Π_{3/2} and X^{2}Σ^{+}B^{2}Σ_{1/2}^{+}absorption spectra. 

The potential energy surface of Li_{2}^{+}(X^{2}Σ_{g}^{+}) alkali dimer colliding with the Xe atom 
S. Saidi^{1}, C. Ghanmi^{1}, F. Hassen^{2} and H. Berriche^{*1,3}
^{1}Laboratoire de Physique et Chimie des Interfaces, Département de Physique, Faculté des Sciences de Monastir, Avenue de l’Environnement, 5019 Monastir, Tunisia.
^{2}Laboratoire de Physique des Semiconducteurs et des Composants Electroniques, Faculté des Sciences, Avenue de l’environnement, 5019 Monastir, Tunisie
^{3}Physics Department, College of Science, King Khalid University, P. O. Box 9004, Abha, Saudi Arabia
^{*}Corresponding author: hamid.berriche@fsm.rnu.tn, hamidberriche@yahoo.fr

The potential energy surface describing the collision between Li_{2}^{+}(X^{2}Σ_{g}^{+}) alkali dimer and the Xenon atom have been calculated for the equilibrium distance of the Li_{2}^{+}(X^{2}Σ_{g}^{+}) and for an extensive range of the two Jacobi coordinates, R and γ. We have used an ab initio approach based on nonempirical pseudopotential and a parametrized ldependent polarization potential [1]. The corecore interactions for Li^{+}Xe is included using the (CCSD(T)) accurate potential of Lozeille et al [2]. This numerical potential is interpolated using the analytical form of Tang and Toennies [3] for a better description of the interactions at intermediate and large distances between Li+ and Xe. This technique has reduced the number of active electrons of Li_{2}^{+}(X^{2}Σ_{g}^{+})Xe system to only one active electron. The ThreeBody interactions are also considered in this calculation and an analytical fitting of the potential energy surface has been realized. To our knowledge, there are neither experimental nor theoretical studies on the collision between the Li_{2}^{+}(X^{2}Σ_{g}^{+}) alkali ionic molecule and the Xenon atom. Therefore, our results are presented here for the first time. In addition the analytical potential energy surface will be used to investigate solvation of Li_{2}^{+} ionic alkali molecule in Xenon small clusters.
References
[1] Ph. Durand and J. C. Barthelat, theorit. Chim. Acta. 38 (1979) 283.
[2] Lozeille et al, Phys. Chem. Chem. Phys. 4 (2002) 3601)
[3] K. T. Tang and J. P. Toennies, J. Chem. Phys. 80 (1984) 3726.


Solvation of Li_{2}^{+}(X^{2}Σ_{g}^{+}) in small Xe_{n} clusters: structure and stability 
S. Saidi^{a}, C. Ghanmi^{a}, F. Hassen^{b} and H. Berriche^{*a,c}
^{a}Laboratoire de Physique et Chimie des Interfaces, Faculté des sciences, Université de de Monastir, Avenue de l’Environnement, 5019 Monastir, Tunisie
^{b}Laboratoire de Physique des Semiconducteurs et des Composants Electroniques, Faculté des Sciences, Avenue de l’environnement, 5019 Monastir, Tunisie
^{c}Physics Department, College of Science, King Khalid University, P. O. B. 9004, Abha, Saudi Arabia
^{*}Email address: hamidberriche@yahoo.fr 
The structure and geometries of the small Li_{2}^{+}(X^{2}Σ_{g}^{+})Xe_{n} clusters taken in different geometries with special symmetry groups, are examined. A oneelectron pseudopotential approach is used to generate the potential energy surface of the Li_{2}^{+}Xe triatomic system for a fixed distance between the two Li alkali atoms (the Li_{2}^{+} equilibrium distance) and for different angles and distances between the Xenon and the Li_{2}^{+} center of mass. In this approach, the effect of the Li+ core and the electronXe interactions are replaced by effective potentials. This has permitted to reduce the number of active electrons of the triatomic system to only one valence electron. In addition, the Li_{2}^{+}Xe interactions are introduced using an analytical form to describe the collision between the alkali ionic dimer and the Xe atom. However, a LennardJones form is used for the XeXe interactions and then included in the total potential energy surface describing the Li_{2}^{+}Xe_{n} cluster. The optimized and stable geometries are performed using the MonteCarlo Bassin Hoping method. This study has shown that the optimal structures correspond to those where Xenon atoms are aggregated on one or both ends of Li_{2}^{+} dimer.
Key words: Pseudopotential, Microsolvation of clusters, MonteCarlo, Structure, 

Spin states in Transition Metal Compounds 
A.M. Pradipto^{1}, R. Maurice^{2,3}, A. Rudavskyi^{1},
Nathalie Guihéry^{2}, C. de Graaf ^{1,3,4} C. Sousa^{5}, and R. Broer^{1}
^{1}Zernike Institute for Advanced Materials, University of Groningen, The Netherlands
^{2}Laboratoire de Chimie et Physique Quantiques, Université de Toulouse 3, France
^{3}Departament de Quimica Fisica i Inorganica, Universitat Rovira i Virgili, Tarragona, Spain
^{4}Institucio Catalana de Recerca i Estudis Avancats (ICREA), Barcelona, Spain
^{5}Dept. Quımica Fisica, Universitat de Barcelona, Spain

Many transition metal compounds show technological useful properties like temperature dependent magnetism or multiferroicity. These properties are in many cases sensitive to external stimuli and believed to be connected to local distortions in the material. In some cases different electronic states seem to coexist
It is a challenge to analyze the competing mechanisms that determine such intriguing properties. The properties are in many cases intimately connected to the open shell character of the transition metals that are present in the materials. Also, spinorbit coupling often plays an important role. Advanced wave function based quantum chemical methods are therefore well suited to study the materials. We use embedded cluster models in which only a small part of the materials is represented in detail. We compare our results with periodic models that lead to band theory.
Our approach [1] will be illustrated with a current study of the magnetic interactions of cupric oxide, CuO. which is a good candidate in the search of high temperature magnetoelectric multiferroics. In a second example we investigate the mechanisms involved in the optical control of the magnetic properties of Fe(II) based spin crossover compounds.
[1] R. Maurice, A.M. Pradipto, N. Guihery, R. Broer, C. de Graaf, J. Chem. Theory Comput. 2010, 6, 30923101.


Examining the Limits of Physical Theory:
Analytical Principles and Logical Implications

Erkki J. Brändas
Department of Physical and Analytical Chemistry
Quantum Chemistr
Uppsala University
SE751 20 Uppsala, Sweden

Our aim is to examine the characteristics and the rationale for developing an analytic foundation for rigorous extensions of quantum mechanics beyond its longestablished domain in physics, chemistry and biology. Paradoxical and inconsistent issues related to the various attempts to apply microscopic organization to derive scientific laws in the macroworld are considered. The theoretical framework is augmented with quantum logical principles via a reformulation of Gödel’s theorems. We arrange the assemblage of the mathematical ideas as follows. First we give a detailed examination of the second order differential equation with respect to specific boundary conditions and associated spectral expansions, followed by a description in terms of general complex symmetric representations exemplified and derived from dilation analytic transformations. Associated dynamical time scales are represented and investigated via the corresponding Dunford formula. Relevant applications are reviewed and compared with conventional scattering theory analysing the directive performance and stability of the method. The manifestation and generation of triangular Jordan block entities are derived and further investigated in thermally excited scattering environments of open dissipative systems. Illustrative applications to condensed and soft condensed matter are provided, and a surprising treatment is given to the Einstein laws of relativity. As a conclusion we emphasize the computational and model building advantages of a conceptual extension of quantum mechanics to rigorously incorporate universal complex resonance structures, their life times and associated localization properties. We also prove the appearance of nonconventional time evolution including the emergence of Jordan blocks in the propagator, which leads to the origin of socalled coherent dissipative structures derived via uniquely defined spatiotemporal neumatic units. This organization yields specific information bearing transformations, cf. the Gödel encoding system, which might connect developmental and building matters with functional issues within a biological framework at the same time providing background dependent features of both special and general relativity theory. 

Coupledcluster methods for molecular solutes described with the framework of the Polarizable Continuum Model. 
Roberto Cammi
Dipartimento di Chimica, Universitŕ di Parma, Parma, ITALY 
A major concern of the modern Quantum Chemistry is the study of molecular properties and processes in solution. One of the most effective approach for the description of solvation effects makes uses of a representation of the solvent as continuum responsive distribution. Considering an abinitio QM description of the solute, the procedure is based on the definition of an effective Hamiltonian which contains a solutesolvent interaction operator of integral type with a two body kernel. The corresponding effective Schroedinger equation is nonlinear and its solution requires a suitable generalization of the standard procedures of abinitio calculation in gasphase.
Within the several version of continuous solvation model, the Polarizable Continuum Model of Tomasi and coworker [1,2] is one of the most popular, due to its capability to treat in an unified computational framework solvent effects on the electronic structure, geometry and a wide range of other molecular properties, at various QM levels. However, only recently the PCM has been extended to the abinitio coupledcluster level [37]. In this talk we describe the basic features involved in this extension, including:
1.analytical gradients for ground and excited electronic states,
2.the study of the excited states by using the SACCI and EOMCC approaches,
3.the linear response functions for the evaluation of dynamical properties of molecular solutes.
References
[1] Miertus, S., Scrocco, E., Tomasi, J., Chem. Phys. 55(1981),117.
[2] J. Tomasi, B. Mennucci and R. Cammi, Chem. Rev., 105(2005)2999.
[3] Cammi, R., J. Chem. Phys., 131(2009),164104.
[4] Cammi, R., Fukuda, R., Ehara, M., Nakatsuji, H., J. Chem. Phys., 133(2010),024104.
[5] Cammi, R., Int. J. Quantum. Chem., 110 (2010),3040.
[6] Fukuda, R., Ehara, M., Nakatsuji, H., Cammi, R., J. Chem. Phys., 134(2011),104109.
[7] Cammi, R., Int. J. Quantum. Chem., submitted


A sequential QM/MM study of the absorption spectrum of vitamin B12 cyanocobalamin in explicit water environment. 
Paula Jaramillo, Kaline Coutinho and Sylvio Canuto
Instituto de Física, Universidade de Săo Paulo, Săo Paulo, Brazil 
The cobaltcorrin ring is the basic unit of the vitamin B12 coenzymes which catalyses radical rearrangements and methyl transfer in biological systems [1]. Their enzymatic activities are based on the properties of a unique CoC bond. This organometallic compound has interesting physical and biological properties. Because of its great biological importance [1,2] several theoretical studies have been performed, but mostly restricted to the central ring. In this work, the absorption spectrum of the full vitamin cyanocobalamin B12 in water is calculated with the sequential QM/MM method. The experimental spectrum in water [2] shows two bands: the intense gamma band near 350 380 nm and the combined alphabetha bands between 460560 nm. Different procedures using continuum, discrete and explicit solvent models were used to include the solvation effect on the calculated absorption spectrum. The discrete and explicit models used Monte Carlo simulation [3] to generate the liquid structure. INDO/CIS (ZINDO) and TDDFT calculations were performed to obtain the excitation energies. Two different functionals, B3LYP and BP86, were used for the spectrum calculations with continuum and discrete models. The explicit model was able to correctly describe the experimental betha and gamma bands, but the low lying alpha band is not obtained with the B3LYP functional. The BP86 calculations give a qualitative and quantitative description with differences between 4 and 10 nm in comparison with the experimental bands. The best result was obtained with the discrete model where the full vitamin B12 is calculated embedded in the electrostatic field of 2000 water. This work gives a good theoretical description and consequently strongly emphasizes the importance of considering the full molecular structure and the role of the solvent in the absorption spectrum of the vitamin B12.
References
[1] K. L. Brown. Chem. Rev. 105, 205 (2005)
[2] T. A. Stich, A. J. Brooks, N. R. Buan, T. C. Brunold. J. Am. Chem. Soc. 125, 5897 (1996)
[3] K. Coutinho, S. Canuto. J. Chem. Phys. 113, 9132 (2000).


Use of Mixed PlaneWave and Gaussian Basis Sets in Electron Scattering Theory and Mainstream Quantum Chemistry 
Petr Carsky
J. Heyrovsky Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Prague, Czech Republic 
In approaches to electron scattering by polyatomic molecules there is a need to evaluate integrals of the types (kk’gg’), (kgk’g’) and (kgg’g’’), where k symbols stand for planewave functions and g’s are gaussians. FűstiMolnár and Pulay^{1} came with an idea that the use of mixed planewave and Gaussian basis sets may also be profitable in the mainstream quantum chemistry, claiming that „modern computers have overcome the severe memory limitations of their predecessors, and thus alternative basis sets such as plane waves are becoming attractive alternatives“. The purpose of this contribution is to show that progress achieved^{2} in efficient evaluation of Coulomb integrals (kk’gg’) in electron scattering theory may also be profitable for the mainstream quantum chemistry.
1. L. FűstiMolnár, P. Pulay: J. Chem. Phys. 116, 7795 (2002).
2. P. Čársky: J. Phys.B 43, 175203,175204 (2010).


Supramolecular Organization and Charge Transport Properties of SelfAssembled pi–pi Stacks of Perylene Diimide Dyes 
Julien idé^{1}, Frédéric Castet^{1}, Raphaël Méreau^{1}, and Laurent Ducasse^{1}
Yoann Olivier^{2}, Nicolas Martinelli^{2}, Jérôme Cornil^{2}, and David Beljonne^{2}
^{1} Université de Bordeaux, Institut des Sciences Moléculaires, 351 Cours de la Libération, 33405 Talence, France
^{2} Laboratory for Chemistry of Novel Materials, University of Mons, Place du Parc 20, B7000 Mons, Belgium

Molecular dynamics simulations have been coupled to Valence Bond/Hartree Fock (VB/HF) quantumchemical calculations to evaluate the impact of diagonal and offdiagonal disorder on charge carrier mobilities in selfassembled onedimensional stacks of a perylene diimide derivative. The relative distance and orientation of the PDI cores probed along the MD trajectories translate into fluctuations in site energies and transfer integrals that are calculated at the VB/HF level. The charge carrier mobilities, as obtained from time of flight numerical simulations, span several orders of magnitude depending on the relative timescales for charge versus molecular motion. Comparison to experiment suggests that charge transport in the crystal phase is limited by the presence of static defects. 

Predicting and interpreting the nonlinear optical responses of complex systems 
Benoît CHAMPAGNE
Laboratoire de Chimie Théorique, UCPTS, Facultés Universitaires NotreDame de la Paix, Rue de Bruxelles, 61, B5000 Namur, BELGIUM, benoit.champagne@fundp.ac.be 
This talk will tackle the problem of predicting and interpreting the nonlinear optical (NLO) responses of complex systems by using quantum chemistry approaches. β and γ, the first and the second hyperpolarizabilities are delicate quantities to predict and reliable (qualitative and/or quantitative) predictions require i) to account for the effects of electron correlation, ii) to choose a sufficiently extended basis set, iii) to include the frequency dispersion effects, iv) to evaluate the vibrational contributions, and v) to describe the interactions with the surrounding. Some of these aspects will be highlighted, starting from model compounds and going to complex systems, including NLO molecular switches, helical chains, ferroelectric liquid crystals, and fluorescent proteins. 

Ab initio calculations of methane dimer interaction energies and
molecular dynamics simulation of fluid methane

Arvin HuangTe Li and Sheng D. Chao
Institute of Applied Mechanics, National Taiwan University, Taipei 106, Taiwan ROC.

Intermolecular interaction potentials of the methane dimers have been calculated for 12 symmetric conformations using the secondorder MřllerPlesset (MP2) perturbation theory and the coupledcluster with single and double and perturbative triple excitations (CCSD(T)) theory. With increasing basis size, a large basis set (augccpVTZ) is required to converge the binding energy at a chemical accuracy (~0.01 kcal/mol). Only the BSSE corrected results systematically converge to the destined potential curve with increasing basis size. The binding energy calculated and the equilibrium bond length using the CCSD(T) method are close to the results at the basis set limit. For molecular dynamics (MD) simulation, a 4site potential model with sites located at the hydrogen atoms was used to fit the ab initio potential data. MD simulations using the ab initio PES show good agreement on both the atomwise radial distribution functions and the selfdiffusion coefficients over a wide range of experimental conditions. 

Ultrafast electronic motion in hydrogen molecular ion induced by a high power intense laser 
H. Mineo^{1} , Y. Teranishi^{2} , S.D. Chao^{1}, and S.H. Lin^{3,4}
^{1} Institute of Applied Mechanics, National Taiwan University, Taipei 106, Taiwan ROC
^{2} Department of Physics, National Chiao Tung University, Hsinchu 300, Taiwan
^{3} Institute of Atomic and Molecular Sciences, Academia Sinica, P. O. Box 23166, Taipei 106, Taiwan ROC
^{4} Institute of Applied Chemistry, Institute of Molecular Science, ChiaoTung University, HsinChu, Taiwan ROC

In this report we show how to control the electronic localization in a molecular ion on attosecond time scale by high intense laser based on two different excitation mechanisms, i.e., one takes place during ionization, and the other one sequentially takes place after the ionization [1]. The electronic excited states of hydrogen molecular ion are created during the ionization by taking the configuration interaction (CI) mixing of neutral molecule into account. Photoionization process is calculated by the generalized KeldyshFaisalReiss (KFR) theory [2]. We detect ultrafast oscillatory electronic motion between two atoms in a hydrogen molecular ion due to the creation of excited states during the ionization.
[1] H. Mineo, Y. Teranishi, S.D. Chao, and S.H. Lin, CPL 499, 45 (2010).
[2] L. V. Keldysh, Sov. Phys. JETP 20, 1307 (1965); F. H. M. Faisal, J. Phys. B6, L89 (1973); H. R. Reiss, Phys. Rev. A22, 1786 (1980).


Catalyst Design: What Can We Learn from Enzymes and Biological Modeling? 
Thomas R. Cundari and Mary E. Anderson
Department of Chemistry, CASCaM, University of North Texas, Denton, TX 76203, United States.
Department of Chemistry and Physics, Texas Woman’s University, Denton, TX 76204, United States. 
Tremendous advances in computational studies of transition metal catalysis have been made in the past decade. In essence, computational inorganic and organometallic chemistry have transformed from a "reactive" to "proactive" endeavor. However, a considerable amount of research effort continues to focus on the refinement of existing catalysts. Much remains to be done to truly develop catalyst design strategies, especially for catalysis for which there is currently no good solution, e.g., methane partial oxidation or carbon dioxide reduction. This presentation will focus on our group's current research in catalysis. Additionally, attention is given to the modeling of Nature's ultimate catalysts  enzymes  in particular, what lessons may be learned and applied to the design of organometallic and inorganic catalysts. 

POTENTIAL ENERGY SURFACES AND DYNAMICS OF SMALL H_{2n+1}^{+} CLUSTERS 
G. Delgado Barrio, P. Barragán, R. Pérez de Tudela, R. Prosmiti, and P. Villarreal
Instituto de Física Fundamental, CSIC, Serrano 123, 28006 Madrid, Spain 
Results of recent studies on the H_{2n+1}^{+} clusters will be presented. Nowdays for the first members of this series high accurate ab initio electronic structure calculations can be carried out. However, a reliable global representation of even the H_{5}^{+} PES is still an open and challenging problem [1]. Thus, here an alternative approach following the idea of ab initio molecular dynamics simulations, that combines nuclear dynamics methods with firstprinciples electronic structure calculations within the DFT framework is adopted. Such DFT approach using the B3(H) hybrid functional, specially designed for hydrogenonly systems, allows to carry out reliable dynamics calculations, classical/quantum mechanical ones, by computing the potential value at a given configuration, on the fly, with both reasonable accuracy and at low computational cost without any posterior parametrization procedure of the surface [2]. It was found that the DFT/B3(H) approach provides a reliable global description of the potential surface of the H_{5}^{+} cluster Based on the B3(H) surface both classical and path integral Monte Carlo (CMC,PIMC) calculations at low temperature are carried out to investigate quantum effects on the internal proton transfer (see figure (b)), and thermal structural fluctuations on the vibrational zeropoint structure of H_{5}^{+} cluster [3]. Such findings are of particular interest for studying larger species of the H_{n}^{+} clusters, as well as gasphase solvation effects, cluster fragmentation, and collision processes in astrophysical applications[4,6].
References
[1] A. Aguado, P. Barragán, R. Prosmiti, G. DelgadoBarrio, P. Villarreal, and O.Roncero J. Chem. Phys. 133, 024306 (2010).
[2] P. Barragán, R. Prosmiti, O. Roncero, A. Aguado, P. Villarreal, and G. DelgadoBarrio, J. Chem. Phys. 133, 054303 (2010).
[3]R. Pérez de Tudela, P. Barragán, R. Prosmiti, P. Villarreal, and G. DelgadoBarrio, J. Phys. Chem. A 115(2011)2483
[4] P. Barragán et al. Phys.Scr. 2011 In press
[5] R. Prosmiti et al., J. Phys. Chem. A 107, 4768 (2003)
[6] P. Barragán et al., (in preparation) 

Valence XPS and Raman Spectral analysis of chitosan film modified by Kr^{+} ion beam bombardments by quantum chemical calculations 
K. Endo^{1}, H. Shinomiya^{1}, T. Ida^{2}, S. Shimada^{2},K. Takahashi^{1}, Y. Suzuki^{3}, H. Yajima^{1}
^{1}Center for Colloid and Interface Science, Tokyo University of Science, 13 Kagurazaka, Shinjukuku, Tokyo 1628601 Japan,
^{2}Laboratory of Theoretical Chemistry, Graduate School of Natural Science and Technology, Kanazawa University, Kanazawa 9201192, Japan,
^{3}Advanced Development and Supporting Center, RIKEN, 21 Hirosawa, Wako, Saitama, 3510198, Japan 
Valence Xray photoelectron and Raman spectra of chitosan film modified by Kr^{+} ion beam bombardments were analyzed from quantum chemical calculations. Experimental Raman spectra of the Kr^{+} ion bombarded film were foundout to be due to four component contributions of chitosan (Chito), diamondlike carbon (DLC), graphite carbon (GC) and amorphous carbon (AC). By considering the four components contribution, we performed depth profile assignments of nm and μm orders for the chitosan film in valence XPS and Raman experiments, respectively from MODFT hybrid calculations in GAUSSIAN 09 using the model molecules of the four components. Carbonizations of the film by Kr^{+} irradiation were obtained as Chito: DLC: AC : GC = 2:1:0.5:0.375 in the μm order from Raman shift spectral analysis, while they were determined as Chito: DLC: AC : GC = 2:1:1:2 in the nm order from valence XPS analysis.
References
[1] K. Takahashi, R. Shizume, K. Uchida, H. Yajima, J. Biorheol, 21,64(2009).
[2] S. Danielache, M. Mizuno, S. Shimada, K. Endo, T. Ida, K. Takaoka, E.Z. Kurmaev, Polym. J. 37,2129(2005).
[3] K. Tamura, K. Endo, Y. Takagi, K. Kato, D. Matsumoto, T. Ida, M. Mizuno, Y. Suzuki, K. Takahashi, K. Uchida, H. Yajima, J. Surf. Anal. 14, 344347(2008).
[4] Gaussian 09, Revision B.01, http://www.gaussian.com.


Valence XPS, IR,and C13 NMR Spectral analysisof 6 polymers by quantum chemical calculations 
Kazunaka Endo^{1}, Tomonori Ida^{2}, Shingo Shimada^{2}
^{1}Research Center for Colloid and Interface Science, Tokyo University of Science 13, Kagurazaka, Shinjukuku 1628601, Japan,
^{2}Laboratory of Theoretical Chemistry, Graduate School of Natural Science and Technology, Kanazawa University, Kanazawa 9201192, Japan 
Valence XPS, IR, and C13 NMR spectra of 6 polymers (PE, PS, PMMA, PET, Nylon6, PVC) have been analyzed by quantum chemical calculations using the polymer model oligomers from B3LYP/631G** basis calculations in GAUSSIAN 09. Simulated valence XPS, IR, and C13 NMR spectra of PS as an example are in good accordance with the experimental results.
References
[1] Gaussian 09, Revision B.01, http://www.gaussian.com.
[2] K. Endo, Y. Kaneda, H. Okada, D. P. Chong, P. Duffy, J. Phys. Chem.,100, 19455 (1996).
[3] Scott A.P., Radom L., J. Phys. Chem., 100, 16502 (1996). 

Laserinduced Electronic and Nuclear Coherent Motions of Chiral Molecules 
Yuichi Fujimura
Department of Chemistry, Tohoku University, Sendai, Japan
Department of Applied Chemistry, National Chaio Tung University, Hsinchu, Taiwan 
Results of a theoretical study of ultrafast laserinduced electronic and nuclear coherent motions of chiral molecules were presented. We have recently found by quantum dynamical simulations that transient unidirectional motions of &pielectrons in an ansa (planarchiral) aromatic ring molecule can be created along its ring by using ultrafast, linearly polarized UV laser pulses. Unidirectional rotational motions, clockwise or counterclockwise, can be controlled by changing the direction of the photon polarization of the pulses. We have also found by nuclear wavepacket simulations that nonadiabatic couplings are directly related to the rotational direction of &pielectrons. In this report, we clarify the nonadiabatic coupling effects on the coherent dynamics of chiral aromatic molecules. 

Second Hyperpolarizabilities of OpenShell Singlet Extended Metal Atom Chains (EMACs) 
Hitoshi Fukui,^{1} Yudai Inoue,^{1} Yasuteru Shigeta,^{1} Benoît Champagne^{2} and Masayoshi Nakano^{1}
^{1}Graduate School of Engineering Science, Osaka University, Japan
^{2}Laboratoire de Chimie Théorique, Facultés Universitaires NotreDame de la Paix (FUNDP), Belgium 
We have theoretically investigated openshell singlet molecules as a novel class of nonlinear optical (NLO) systems, and have revealed their structure−property relationship: singlet diradical systems with intermediate diradical characters (y) tend to exhibit larger second hyperpolarizabilities (γ) than pure diradical and closedshell systems [1,2]. In addition to organic compounds, polynuclear transition metal complexes are expected to show singlet multiradical nature due to the unpaired electrons in the metal dorbitals [3]. In particular, openshell singlet extended metal atom chains (SEMACs), which have metal−metal direct bonds between transition metal atoms are promising NLO candidates because of the extended d−d conjugation and the singlet multiradical characters originating from the interactions between the dorbitals, which can create dσ, dπ and dδ electron conjugation. In the present study, we theoretically investigate the multiradical characters of the dσ, dπ and dδ orbitals as well as the γ values of SEMACs of chromium(II) without ligands. We also analyze the contributions of these orbital electrons to γ [γ(dX), where X = σ, π or δ] in order to reveal relationships between the orbital symmetry, the multiradical character and the γ value.
[1] M. Nakano et al., J. Phys. Chem. A 109, 885 (2005).
[2] M. Nakano et al., J. Chem. Phys., 125, 074113 (2006); Phys. Rev. Lett., 99, 033011 (2007).
[3] H. Fukui et al., J. Phys. Chem. Lett. 10.1021/jz2007897 (2011). 

Origin of Antiferromagnetism in Molecular and Periodic Systems
in Original KohnSham Local Density Approximation 
Kimichika FUKUSHIMA
Department of Advanced Reactor System Engineering
Toshiba Nuclear Engineering Service Corporation
8, Shinsugitacho, Isogoku, Yokohama, 2358523, Japan 
This study presents a solution to the issue, which attracted attention due to the discovery of copper (Cu) oxides in 1986, of whether LDA (local density approximation) can describe antiferromagnetism. From an early stage, many LDA band structure calculations failed to reproduce the insulating antiferromagnetic state. The Hubbard model predicts antiferromagnetism in a system for appropriate conditions. The author’s LDA calculations were performed for elongated hydrogen molecules comprising multiple atoms using the discrete variational (DV) molecular orbital method. The LDA employed is the original KohnSham formalism, since the magnetic properties by GGA (generalized gradient approximation) are similar to the original KohnSham results than those by the VWN (VoskoWilkNusair) approximation. The DV method with numerically calculated basis atomic orbitals derived antiferromagnetic ordering for hydrogen molecules at long interatomic separations. The DV method for Cu oxide molecules looked as if the method could not describe antiferromagnetism, where a well potential with a usual depth of about 1 Hartree within an ionic radius was added solely to the potential for generating O^{2} basis atomic orbitals. However, the author finally arrived at the antiferromagnetism description via a reduced well potential depth after long parameter surveys [1,2]. The calculation was generalized to a periodic system CaCuO_{2} using a method employing the Bloch type linear combination of atomic orbitals with all electrons [3]. Furthermore, we determined a spherically averaged well potential depth having originated from the Coulomb potential by the nucleus and electron clouds around O^{2} in a solid. The system revealed the antiferromagnetic ordering due to a shallow well depth. Since the Coulomb potential induced well for the anionic basis set is general, this method is applied to molecular orbital calculations.
References
[1] K. Fukushima, J. Phys. Soc. Jpn. 69 (2000) 1247.
[2] K. Fukushima, Adv. Quant. Chem. 54 (2008) 47.
[3] K. Fukushima, Int. J. Quant. Chem. (2011) DOI: 10.1002/qua.23146.


Finite Fermi Systems in Strong External DC Electric and Laser Fields: New Quantum Approach

Alexander V. Glushkov^{1,2}
^{1} Odessa University, Odessa9, SE, Ukraine,
^{2} ISAN, Russian Academy of Sciences, Troitsk, Moscow reg., Russia 
We present new quantum method for studying interaction of the finite Fermi systems (atoms, nuclei, diatomics) with an intense and superintense external fields (DC electric and laser fields). New quantum method is the combined relativistic operator perturbation theory and relativistic energy approach [1,2]. The energy approach is based on the GellMann and Low adiabatic formalism and formalism of the relativistic Green function for the Dirac equation with nonsingular potential and complex energy [2]. The operator perturbation theory formalism includes a new quantization procedure of the KohnShan and Dirac equations states of the finite Fermisystems in a strong field. The key feature is that the zeroth order Hamiltonian, possessing only stationary states, is determined only by its spectrum without specifying its explicit form. Some results of the calculation for the DC, AC strong field Stark resonances, multiphoton resonances, broadening autoionization resonances, ionization profiles for the H, Cs, Yb, Gd atoms are presented and compared with results of other known theories [3]. Especial interest attracts new relativistic treating of the drastic broadening effect of widths for the reorientation decay autoionization resonances in lanthanides [1]. The direct interaction of super intense laser fields in the optical frequency domain with nuclei is studied and the AC Stark effect for nuclei is described within the operator perturbation theory and the relativistic meanfield (plus DiracWoodsSaxon) model for the groundstate calculation of the nuclei 49Sc, 168Er, 171Yb. The results are compared with other available data [3].
References :
[1]. A.V.Glushkov, L.N.Ivanov, Phys.Lett.A.170,36 (1992); J.Phys. B 26, L379 (1993); Preprints ISAN NAS13, Moscow (1992).
[2]. A.V.Glushkov et al, Int.J.Quant.Chem.99, 936 (2004); 104, 562 (2005); 109, 1717 (2009); 111, 286 (2011); Frontiers in Quantum Systems in Chem. and Phys. (Springer), 15, 285 (2006); 18, 505585 (2008), 20, 127 (2009);
[3] E.Brandas, P.Froelich, Phys.Rev.A 16, 2207 (1977); J.Rao, B.Li, Phys.Rev.A 51,4526 (1995); T.Burvenichm J.Evers, C.H.Keitel, Phys.Rev.Lett. 96, 142501 (2006); A.Glushkov, L.N.Ivanov, V.S.Letokhov, Preprint ISAN NAS4, MoscowTroitsk (1991). 

Laser ElectronGammaNuclear Spectroscopy of Atoms and Multicharged Ions and NEET Effects in Heavy Nuclei: Relativistic Energy Approach 
Alexander V. Glushkov,^{1,2} Olga Yu. Khetselius^{1} Svetlana Malinovskaya^{1} and Andrey A. Svinarenko^{1}
^{1}Odessa University, Odessa9, SE, Ukraine
^{2}ISAN, Russian Academy of Sciences, Troitsk, Moscow reg., Russia 
In the resonant process of nuclear excitation by electron transition (NEET) or electron capture (NEEC) an electron is captured into a bound atomic shell with the simultaneous excitation of the nucleus. The excited nucleus can then decay radiatively or by internal conversion. In the latter case, a resonant inelastic electron scattering on the nucleus occurs. Here we present consistent, relativistic approach to calculation of the probabilities of the different cooperative laser electrongammanuclear processes in atoms, ions, nuclei and resonant NEET (NEEC) processes in heavy nuclei, based on the relativistic density functional (DF) formalism and energy approach (Smatrix formalism of GellMann and Low) [2]. Decay and excitation probability is linked with the imaginary part of energy of the excited state for the “electron shell nucleusphotons” system. For radiate decays it is manifested as effect of retarding in interaction and selfaction and calculated within QED DFT theory [2]. We firstly present data about intensities of the electron satellites in gammaspectra of nuclei in the neutral (low lying transitions) and multicharged Oand Flike ions for isotopes 57Fe, 133Cs, 171Yb and discover a new effect of the giant increasing electron satellites intensities under transition from the neutral atoms to multicharged ions. We present new, more accurate data about NEET probabilities in the nuclei of 189Os, 197Au (with comparison with theoretical data by Tkalya and experimantal data of Argonne Nat.Lab. and Japan Synchrotron Centre [3]) and firstly for nuclei of 193Ir, 235U, 268Mt.
References:
[1]. L.N.Ivanov, V.S.Letokhov, JETP. 93, 396 (1987); A.V.Glushkov, L.Ivanov, Phys.Lett.A 170, 33 (1992); A.V.Glushkov, L.N.Ivanov, V.S.Letokhov, Preprint of ISAN N AS4, Troitsk, (1992); E.V.Tkalya, Phys.Rev.A.75, 022509 (2007); T.J. Burvenichm J.Evers, C.H.Keitel, Phys. Rev. C. 74, 044601 (2007) ; A.Shahbaz, C.Muller, A.Staudt, T.J.Burvenich, C.H.Keitel, Phys.Rev.Lett.98, 263901 (2007).
[2]. A.Glushkov et al, J.Phys.CS. 11, 188 (2005); 35, 425 (2005); Int.J.Quant.Chem. 104, 512, 562 (2005); 99, 889, 936 (2004); Europ.Phys.Journ. 160, 195 (2009); Phys.Scr.T135, 014022 (2009).
[3]. S.Kishimoto, Y.Yoda, Y.Kobayashi etal, Phys.Rev.C74, 031301 (2006); I. Ahmad, R.Dunfird, H.Esbensen etal, Phys.Rev.C61, 051304 (2000). 

Development of Algorithms and Computer Programs for Performing LargeScale Energy and Dynamics Calculations for the Excited States of Molecular Systems on Graphical Processing Units 
Jeffrey R. Gour, Nathan Luehr, Christine M. Isborn, Ivan S. Ufimstev, Todd J. Martinez
PULSE Institute and Department of Chemistry, Stanford University, CA 94305
SLAC National Accelerator Laboratory, Menlo Park, CA 94305

Chemical reactions on excited electronic states play a significant role in many important processes of scientific interest, including biological photoreceptors and lighttriggered or lightpowered molecular devices. Unfortunately, thanks to long computer times and high disk and memory requirements, the ability to study these processes for large molecular systems with ab initio methodologies is severely restricted. In order to overcome such limitations, allowing one to perform ab initio excitedstate energy, property, and dynamics calculations for larger systems than previously possible, we have recently developed new implementations of the configuration interaction singles (CIS) and TammDancoff timedependent density functional theory (TDATDDFT) approaches which utilize massively multiparallel graphical processing units (GPUs) in the calculation of energies [1] and gradients.
In this presentation, some of the details of the implementations developed in this work, which are included in the development version of the TeraChem software package, will be discussed. Following the structure of the previously developed HartreeFock and KohnSham DFT GPU implementations [13], these programs utilize a direct algorithm, in which the oneelectron matrix elements and twoelectron coulomb integrals, as well as the corresponding gradient elements, are computed on the fly using the GPU, greatly reducing the computational cost of the calculation. To illustrate the performance and speedups provided by these implementations, benchmark energy and geometry optimization calculations are performed for four generations of oligothiophen dendrimers as well as for photoactive yellow protein (PYP). In addition, we use these codes to perform ab initio multiplespawning dynamics for PYP and GFP, using the reduced computational cost to investigate the effect of increasing the size of the QM region in the QM/MM calculation relative to that of previous studies.
[1] C.M. Isborn, N. Luehr, I.S. Ufimtsev, and T.J. Martinez, J. Chem. Theory Comput. Submitted.
[2] Ufimtsev, I. S.; Martinez, T. J., J. Chem. Theory Comput. 2009, 5, 1004.
[3] Ufimtsev, I. S.; Martinez, T. J., J. Chem. Theory Comput. 2009, 5, 2619.


Exact factorization of the timedependent electronnuclear wavefunction 
E.K.U. Gross
Max Planck Institute for Microstructure Physics, Weinberg 2, D06120 Halle (Saale), Germany 
The coupling between electronic and nuclear motion plays an important role in a variety of phenomena. Prominent examples are superconductivity, the process of vision, and photosynthesis. Standard approximations such as Ehrenfest dynamics, surface hopping, or nuclear wavepacket dynamics only partially capture the nonadiabatic effects. As a first step towards a full abinitio treatment of the coupled electronnuclear system, we deduce an exact factorization of the complete wavefunction into a purely nuclear part and a manyelectron wavefunction which parametrically depends on the the nuclear configuration. We derive formally exact equations of motion for the nuclear and electronic wavefunctions [1]. These exact equations lead to a rigorous definition of timedependent potential energy surfaces as well as timedependent geometric phases. With the example of the hydrogen molecular ion in a laser field we demonstrate the significance of these concepts in understanding the full electronion dynamics. In particular, the timedependent potential energy surfaces are shown to represent a powerful tool to analyse and interpret different (direct vs. tunneling) types of dissociation processes.
[1] Ali Abedi, Neepa T. Maitra, E.K.U. Gross, PRL 105, 123002 (2010).


Elongation Method Applicable to Nonlinear Optics: TOWARDS LINEAR SCALING 
Feng Long Gu^{1,2}
^{1}Center for Computational Quantum Chemistry, South China Normal University, Guangzhou, Guangdong 510631, China;
^{2}CREST, Japan Science and Technology Agency (JST), Kawaguchi, Saitama, Japan

The elongation method is presented for linear scaling HartreeFock electronic structure calculations of periodic and/or aperiodic systems. The elongation method uses regional localization of molecular orbitals, instead of canonical molecular orbitals. The accuracy and timing of the method is demonstrated for several systems of interest such as polyglycine and BN nanotubes. Based on the high accuracy/efficiency elongation method for studying bioand nanosystems, formulas for calculating nonlinear optical (NLO) properties of large systems are derived. First of all, it is to work out the formulas for localized molecular orbitals in the presence of external electric field, and then derive the elongation timedependent HartreeFock (TDHF) equations. Finally, find the solution of the localized TDHF equations. The application is going to work out a program package to determine the NLO properties for large systems with high accuracy (error less than 10^{6} au) and high efficiency (linear scaling or better). It is then applied to the NLO properties for biomolecules, polymers, and nanomaterials. It is expected to provide a tool for designing NLO materials and studying physical/chemical properties of huge systems.
[References]
[1] “Elongation Method for Polymers and its Application to Nonlinear Optics, in Atoms, Molecules and Clusters in Electric Fields: Theoretical Approaches to the Calculation of Electric Polarizabilities”, Feng Long Gu, Akira Imamura, and Yuriko Aoki, (edited by G. Maroulis, Imperial College Press), Vol. 1, Page 97177, 2006.
[2] F. L. Gu, Y. Aoki, A. Imamura, D. M. Bishop, and B. Kirtman, Mol. Phys. 101 (2003) 1487.
[3] S. Ohnishi, F. L. Gu, K. Naka, A. Imamura, B. Kirtman, and Y. Aoki, J. Phys. Chem. A, 108 (2004) 8478. 

Bonding in negative ions:
The role of d orbitals of third period or heavier atom

Balázs Hajgató,^{1} Frank De Proft,^{1} David J. Tozer, ^{2} Paul Geerlings,^{1} and László Nyulászi^{3}
^{1}Eenheid Algemene Chemie (ALGC), Member of the QCMM Research Group – Alliance GhentBrussels, Vrije Universiteit Brussel (VUB), Pleinlaan 2, B1050 Brussels, Belgium
^{2}Department of Chemistry, University of Durham, South Road, Durham, DH1 3LE UK.
^{3}Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Gellért tér 4, H–1521, Budapest, Hungary; Materials Structure and Modeling Research Group of the Hungarian Academy of Sciences, Budapest University of Technology and Economics, Szt. Gellért tér 4., Budapest, H1111, Hungary

In the early 90's it has been shown that dorbitals do not participate in the bonding of neutral molecules containing heavy atoms [1]. This founding is in agreement with the ionization energies of the pyridinestibabenzene series obtained by photoelectron spectroscopy, where the A_{2} ionized states have almost constant energy within the series [2]. Since the a_{2} orbitals have two planar nodes through the heteroatom, they are relatively unperturbed by the heteroatom, and a dorbital interaction would stabilize an A_{2} cationic state. In contrast to this, the electron transmission investigation of the electron affinities of the same series [3] revealed that A_{2} π* anionic state of phosphabenzene is stabilized by about 0.5 eV with respect to pyridine, while it remains almost constant for arsabenzene and stibabenzene, i.e., in all those compounds where the heteroatom have dorbitals in the valence shell.
We have investigated the dorbital contribution in the semioccupied molecular orbitals of the pyridinestibabenzene and furantellurophene series in both lowlying ^{2}A_{2} and ^{2}B_{1} anionic states by means of a newly developed, "potential wall confinement" technique [4]. We found a significantly increase in the heteroatom dorbital contributions of the semioccupied a_{2} orbitals in the P, As, Sb and the S, Se, Te compounds, compared to the N and O compounds. The trends in the case of B_{1} anionic states are the same, however, due to symmetry reasons the heteroatom perturbs the b_{1} orbitals more significantly than the a_{2} orbitals [5].
[1] A. E. Reed, P. v. R. Schleyer, J. Am. Chem. Soc., 112, 1434 (1990); E. Magnusson, J. Am. Chem. Soc., 115, 1051 (1993)
[2] C. Batich, E. Heilbronner, V. Hornung, A. J. Ashe III., D. T. Clark, U. T. Cobley, D. Kilcast, I. Scanlan, J. Am. Chem. Soc., 95, 928 (1973)
[3] P. D. Burrow, A. J. Ashe III, D. J. Bellville, K. D. Jordan, J. Am. Chem. Soc., 104, 425 (1982)
[4] D. J. Tozer, F. De Proft, J. Chem. Phys., 127, 034108 (2007)
[5] B. Hajgató, F. De Proft, D. Szieberth, D. J. Tozer, M. S. Deleuze, P. Geerlings, L. Nyulászi.
Phys. Chem. Chem. Phys., 13, 1663 (2011)


Enzymeinhibitor interaction : Key Structural and Energetic Properties for Inhibitor Design 
Supa Hannongbua
Department of Chemistry, Faculty of Science, and Center of Nanotechnology, Kasetsart University, Bangkok 10903, Thailand. 
Quantum chemical calculations and ONIOM methods have been used to investigate enzymeinhibitor interaction. The pairwise analyses between efavirenz and individual residue in the binding pocket of both WT and K103N HIV1 RT were calculated and the ONIOM2 methods was used to evaluate the binding energies. The results show that the K103N RT is more repulsive interactions between efavirenz and residues surrounding the binding pocket than of the WT structure. The results from pairwise energies perfectly demonstrate that the K103N RT slightly affect on the loss of interaction energy. The main influences are due to residues around the binding pocket (Lys101, Lys102, Ser105, Val179, Trp229, Pro236 and Glu138). Baesd on ONIOM2 calculations, these evidently show that the K103N decreases the stabilization energy of efavirenz bound to its binding pocket. Furthermore, the analyses of the energy components in terms of interaction energy and deformation energy also shows a significant structural rearrangement upon efavirenz binding, and more energy is needed for conformational adaptation in the binding pocket. The potent inhibitor accommodates the K103N RT by the formation of an additional interaction to the asparagine side chain and minor rearrangement of the inhibitor position in the binding pocket. It is worth to note that the K101 and S105 residues are important as strong interaction for further novel inhibitor development. Taken into account, the K101 residue shows the key main interaction of the binding due to the presence of hydrogen bonding between efavirenz and the backbone of K101. Advantages and disadvantages of the studies, applied on different enzyme targets will be also given.
References
1. Srivab, P. and Hannongbua, S.*, A study of the binding energies of efavirenz to wildtype and K103N/Y181C HIV1 reverse transcriptase based on the ONIOM method, Chem. Med. Chem., 3(5), 803811 ( 2008)
2. Maitarad, P., Kamchonwongpaisan, S., Vanichtanankul, J., Vilaivan, T., Yuthavong, Y., Hannongbua, S.*, Interactions between Cycloguanil Derivatives and WildType and ResistanceAssociated Mutant P. falciparum Dihydrofolate Reductases, J.ComputAided Drug Des., 23(4), 241252 ( 2009)
3. SaeTang, D., Kittakoop, P., and Hannongbua, S., Role of Key Residue Specific to Cyclooxygenase II : An ONIOM Study, Monatsh. Chemie, 140, 15331541 ( 2009).
4. Vailikhit, V, Holzschuh, W.J. and Hannongbua, S., 1HNMR chemical shifts of some DMSOsolvated amines using MDONIOM2, J. Mol.Struct. ( THEOCHEM), 944, 173176 ( 2010).
5. Kittisripanya, N., Wolschann, P., and Hannongbua, S., Binding of Huperzine A and Galanthamine to Acetylcholinesterase, Based on ONIOM Method, Nanomedicine: Nanotechnology, Biology, and Medicine 7, 60–68 ( 2011).
6. Saparpakorn, P., Wolschann, P., Karpfen, A., Pungpo, P., Hannongbua, S., Systematic investigation on the methodology in the binding of GW420867X as NNRTI by using quantum chemical calculations, Monatsch Chemie, ( 2011) in press.
7. Treesuwan, W., H., Hajime, Morokuma, K., and Hannongbua, S.*, Characteristic vibration patterns and protein binding of odor compounds from bread baking volatiles: Density functional, ONIOM study and principle component analysis (PCA), J. Theor.Biol., ( 2011), accepted.
8. Boonsri, P., Kuno, M. and Hannongbua, S.* Key interactions of the mutant HIV1 Reverse Transcriptase/Efavirenz: An evidence obtained from ONIOM method” to you. The response to reviewers has been done according to the reviewers ( 2011) submitted. 

Excited states of photofunctional proteins: SACCI study 
Junya Hasegawa
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University 
In the vision and fluorescent proteins, controlling photoabsorption/emission energy of chromophore is the essential to furnish a protein with the photofunctionality. Retinal Schiff base in vision, luciferin in insects, and greenfluorescent protein chromophores in a jellyfish are the representative compounds in nature. Depending on the molecular interactions with protein environment, these chromophores show a variety of photoabsorption/emission energies.
The present talk summarizes some recent theoretical studies on the spectral tuning mechanism in photobiology using quantum chemical calculations with the symmetryadapted cluster configuration interaction (SACCI) method. SACCI is a coupledcluster method for describing the electron correlations in the ground and excited states. To investigate excited states of chromophores and fluorophores in proteins, we introduced the SACCI method into the QM/MM framework.
We studied spectral tuning mechanism of retinal proteins [1] and emission color tuning of firefly luciferase [2] and fluorescent proteins [3], and found a common feature in their physical origin. Analyzing molecular interactions, we could also clarify amino acids’ contributions to the spectral tuning. On the basis of the mechanisms, we proposed mutations for artificially controlling the color of proteins, which was computationally examined by computational simulations [2,3].
[1] K. Fujimoto, J. Hasegawa, H. Nakatsuji, Bull. Chem. Soc. Jpn., 82 (2009) 11401148. [2] N. Nakatani, J. Hasegawa, H. Nakatsuji, J. Am. Chem. Soc. 129 (2007) 87568765; N. Nakatani, J. Hasegawa, and H. Nakatsuji, Chem. Phys. Letters 469 (2009) 191194. [3] J. Hasegawa, T. Ise, K. Fujimoto, A. Kikuchi, E. Fukumura, A. Miyawaki, and Y. Shiro, J. Phys. Chem. B, 114(8), 29712979 (2010). 

Singlet Fission for DyeSensitized Solar Cells 
Zdenek Havlas^{1}, Josef Michl^{1,2}
^{1}Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nam. 2, 16610 Prague6, Czech Republic
^{2}Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 803090215, United States 
Singlet Fission is a spinallowed process in which a molecular chromophore excited into its singlet state shares energy with a nearby ground state chromophore, producing a pair of triplet excited
chromophores initially coupled into an overall singlet. In a more detailed description, the initial singlet state actually is a coherent superposition of eigenstates of the total Hamiltonian operator that includes electron spinspin and Zeeman interactions that dictate its further fate, along with possible spatial diffusion, internal conversion, intersystem crossing, and other possible competing processes.
Although, the Singlet Fission is known is some special cases of crystalline aromatic hydrocarbons for a half of century, using of this process for increasing of the solar cell efficiency is a new topic. It includes studies of several steps and interplay of theoretical, synthetic, and spectroscopic procedures, namely:
 Selection of the proper chromophore which satisfies the following conditions: E(S_{1}) ≥ 2 E(T_{1}) but also E(T_{2}) ≥ 2 E(T_{1}). We have observed that 1,3diphenylisobenzofuran satisfies these conditions and yields 200% of triplet states in a crystalline state.
 For practical reasons, the S_{1} excitation energy should be around 2.2 eV. Searching for structures with this property is done by extensive set of quantum chemical calculations of excited states. We have already preselected a few structures which have to be now synthesized and studied experimentally.
 For effective Singlet Fission process proper mutual orientation of chomophore pairs is essential. We have developed a simple Hamiltonian model and performed numerical calculations for different orientations of chromophores. The rules for the geometrical requirements resulted from these calculations will be discussed.
 Preparation of a dye with both chromophores in ideal positions, either by selforganization or by synthesis of supermolecule with both chromophores properly arranged in it.
 The final stage requires separation of charges of individual triplet chromophores, transport of the charges to the TiO_{2} semiconductor and injection of the electrons to the semiconductor.
We will report on progress in the first three steps, the last two steps still need to be solved.


Plasmonic excitations of metalatom chain and ring cluster oligomers 
Michitoshi Hayashi
Center for Condensed Matter Sciences, National Taiwan University, Taiwan 
Plasmonic excitations in metallic nanostructures are fascinating phenomena that are not only rich of physics but also finding many technological applications in e.g., biological sensors and solar cells. Therefore it is important to understand the origin and mechanism of these intriguing plasmonrelated phenomena in the metal nanocomposites. In particular, we are interested in how plasmonic excitations can alter the spectroscopy and dynamics of molecules in the vicinity of the metal cluster.
We have recently exploited the interaction between a molecule and the metalatom cluster systems. We take several chromophore molecules and simple metalatom systems. For cluster systems, we further consider two particular structures: chain and ring in order to make clear definition of “plasmonlike” excitation. For finite chain systems, unlike infinite systems, charge localization can be found near both boundaries of the chain, which leads to huge transition dipole moment upon excitation. Therefore electronic excitations of molecules in the vicinity of these two boundaries can be affected. For the normal ring systems, on the other hand, there is no charge localization. The characteristics of the ring system is that singlet state becomes unstable if n=4, 8, 12, 16, …. with n being the number of atom. Thus the system will lower the symmetry (Peilers instability) if singlet state is required while triplet state will be stable if the structure is kept. Thus the interaction with molecules will be more complicated and thus the ring systems may be used to control the optical electronic excitation properties of the molecules.


Are there isoelectronic trends among FranckCondon Factors? 
Ray Hefferlin,^{1} Jonathan Sackett^{1} and Jeremy Tatum^{2}
^{1}Southern Adventist University, Collegedale, TN 37315, USA
^{2}University of Victoria, Victoria, BC V8W 2Y2, Canada 
We have calculated the loci of the strongest bands in the ( v '', v ') plane of band systems for many diatomic molecules, assuming both the simple harmonic oscillator (SHO) approximation and the Morse approximation for the potentials of the electronic states. In the SHO case the Condon loci are parabolas. These descriptions are for ( v '', v ') < (11,11). We have calculated the latera recta and the orientations of the SHO parabolas for transitions appropriate to molecules with 13, 21, and 22 electrons. We find that the angle between the symmetry axis of the Condon parabola and the v '' axis is highest for species one protonshift away from "raregas" molecules, such as LiNe. Our preliminary results are shown here. The raregas molecules are indicated by vertical lines and by parentheses around their names.



Fig. 1. The 13electron molecules are CN, BO, BeF, (LiNe), (NaHe), and MgH.The bands are A^{2}Π^{+}X^{2}Σ.

Fig. 2. The 22electron molecules are Na_{2}, (MgNe), AlF, SiO, PN, SC, BCl, and (BeAr). The bands are A^{1}ΠX^{1}Σ^{+}.

Fig. 3. The 21electron molecules are (NaNe), MgF, AlO, SiN, PC, BS, BeCl, (LiAr), (KHe), and CaH. The bands are B^{2}Σ^{+}X^{2}Σ^{+}.



Theories and applications for electronic coupling in triplet energy transfer 
ChaoPing Hsu
Institute of Chemistry, Academia Sinica 
The transport of charges and excitation energy are two processes of fundamental importance in diverse areas of research. Characterizations of electron transfer (ET) and excitation energy transfer (EET) rates are essential for a full understanding of many biological systems and optoelectronic devices. The electronic coupling factor is an offdiagonal Hamiltonian matrix element between the initial and final diabatic states in the transport processes. ET coupling is essentially the interaction of the two molecular orbitals (MOs) where the electron occupancy is changed. Singlet excitation energy transfer (SET) contains a Förster dipole–dipole coupling term as its most important constituent. Triplet excitation energy transfer (TET) involves an exchange of two electrons of different spin and energy; thus, it is like an overlap interaction of two pairs of MOs.
In the past, we have developed or improved some of the strategies for calculating ET, SET, and TET couplings. In the presentation, I plan to report our recent progresses with a focus on the TET and its application.
With a newly developed computational scheme, the Fragment Spin Difference (FSD), we can calculate the TET coupling over a general class of systems. It is therefore possible to calculate TET coupling values for systems that were previously hard to obtain for a number of reasons. Our recent results on photosynthetic lightharvesting complexes will also be discussed. In particular, TET the bacterial lightharvesting complex II (LH2) of Rhodospirillum molischianum and Rhodopseudomonas acidophila, and the peridininchlorophyll a protein (PCP) from Amphidinium carterae. The TET rates were estimated based on the couplings obtained. For all lightharvesting complexes studied, there exist nanosecond TET from the chlorophylls to the carotenoids. Our result supports a direct triplet quenching mechanism for the photoprotection function of carotenoids. The TET rates are similar for a broad range of carotenoid triplet state energy, which implies a general and robust TET quenching role for carotenoids in photosynthesis. This result is also consistent with the weak dependence of TET kinetics on the type or the number of πconjugation lengths in the carotenoids and their analogs reported in the literature. Our results provide theoretical limits to the possible photophysics in the lightharvesting complexes.


Linearity condition for orbital energies for hybrid functionals 
Yutaka Imamura,^{1} Rie Kobayashi^{1} and Hiromi Nakai^{1,2}
^{1}Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 341 Okubo, Shinjukuku, Tokyo 1698555, JAPAN
^{2}Research Institute for Science and Engineering, Waseda University, 341 Okubo, Shinjukuku, Tokyo 1698555, JAPAN

We propose the linearity condition for constructing an orbitalspecific (OS) hybrid functional. The developed OS hybrid functional provides accurate ionization potentials (IPs) of core and valence orbitals for molecules containing 2nd and 3rd row atoms in the sense of Koopmans' theorem. The reaction barrier and dissociation curves are also well reproduced by the OS hybrid functional.


Luminescence Wavelengths and the Energy Level Structures of Binuclear Copper(I) Complexes 
Tomohiko Ishii,^{1} Masahiro Kenmotsu,^{1} Kiyoshi Tsuge,^{2} Genta Sakane,^{3} Yoichi Sasaki,^{4} Masahiro Yamashita,^{5} and Brian K. Breedlove^{5}
^{1}Department of Advanced Materials Science, Faculty of Engineering, Kagawa University
^{2}Department of Chemistry, Faculty of Science, University of Toyama
^{3}Department of Chemistry, Faculty of Science, Okayama University of Science
^{4}Division of Chemistry, Graduate School of Science, Hokkaido University
^{5}Department of Chemistry, Graduate School of Science, Tohoku University 
Electronic structures and the energy level diagrams of binuclear copper(I) halide complexes exhibiting luminescence ranging from blue to red have been calculated by means of a discrete variational (DV)Xα molecular orbital method. We confirmed that the wavelength of the experimental luminescence could be reproduced by comparing the electronic states of the ground state in relation to the luminescence caused by electron transfer between the excited and the ground states. The observed luminescence wavelength is related to the excitation energy from the occupied copper 3d to the unoccupied ligand molecular orbitals. Therefore, it should be possible to predict the experimental wavelength of the luminescence of their unknown analogues by comparing the excitation energy among them.
In this study, we investigated the differences in the electronic structures among the binuclear copper(I) complexes ([Cu_{2}(μX)_{2}L] (X = Br and I) (L = Nheteroaromatic ligands)) in order to determine the luminescence mechanism and the ligand dependence. The luminescence wavelength was linearly correlated to the energy difference between the metal's 3d orbitals below the HOMO level and the ligand's πconjugated molecular orbitals above the LUMO level. This result is consistent for a system in which luminescence occurs when an electron returns to the ground state after being excited via MLCT. Our analysis can be applied not only to the binuclear copper(I) complexes ([Cu_{2}(μX)_{2}L] mentioned in this paper but also to any other metal complexes showing luminescence. In other words, we can predict the luminescence wavelength of unknown metal complexes in relation to the electronic structures of known complexes. 

Theoretical Study on the Redox Reaction of Azurin in Water Solvent 
Masashi Iwayama, Hiroaki Saito, Kazutomo Kawaguchi and Hidemi Nagao
Division of Mathematical and Physical Science, Graduate School of Natural Science and Technology, Kanazawa University, Japan 
Metalloproteins including a transitionmetal ion in the active site have important characteristics such as the metabolism and the intracellular signaling in vivo. In metalloproteins, Azurin is a kind of blue copper protein containing a copper atom in the active site, and has been known to show the oxidationreduction reaction by charge transfer between the active sites of proteins in the solution. In this study, we carry out molecular dynamics simulations and the quantum mechanics calculations of the oxidized Azurin (Az(Ⅱ)) and reduced Azurin (Az(Ⅰ)) in water solvent to reveal the redox character of Azurin in water solvent. According to the BornHaber Cycle model, the free energy change of the solute molecule in solvent can be expressed as a summation of the free energy change of solute in gas phase and the difference of solvation free energies of the solute. From these results, we estimate of the redox potential of Azurin and compare with the experimental value. 

Dynamics of Large Finite Systems at Extremes 
Joshua Jortner
School of Chemistry
Tel Aviv University
Ramat Aviv
69978 Tel Aviv, Israel 
The exploration of photoinduced ultrafast response, dynamics, reactivity and function in clusters, nanostructures and biological systems pertains to the interrogation and control of the phenomena of energy acquisition, storage and disposal, as explored on the molecular level. We shall focus on recent theoretical and computational studies of finite systems dynamics under extreme energetic and temporal conditions. Ultrafast and ultrahigh phenomena pertain to extreme cluster ionization in ultraintense laser fields (with peak intensities of up to IM = 10^{21} Wcm^{2}, which constitutes the highest light intensity on earth), ultrafast femtosecond dynamics on the time scale of nuclear motion, attosecond–femtosecond electron dynamics, the production of ultrahigh charges in completely ionized molecular or elemental clusters, and the attainment of ultrahigh ion energies (keV–MeV) in Coulomb explosion of multicharged clusters. Coulomb explosion of clusters and nanostructures transcends chemical dynamics towards the driving of nuclear reactions involving tabletop nuclear fusion and nucleosynthesis of astrophysical interest. 

Calculation of Magnetic Properties and Spectroscopic Parameters of Manganese Clusters with Density Functional Theory Methods 
Keita Kanda, Toru Saito, Yasutaka Kitagawa, Takashi Kawakamai, Shushuke Yamanaka, Kizashi Yamaguchi and Mitsutaka Okumura
Graduate School of Science, Osaka University, Japan 
Many manganese complexes bridged by μoxo ligands are synthesized as model of the oxygenevolving complex (OEC) in Photosystem II. Catalytic cycle and oxidation states of Mn cluster in OEC is still unrevealed. Spectroscopic parameters for those model complex, especially hyperfine coupling constants (HFCs) measured by EPR suggest deep insight for electronic structure.
Many calculation of HFCs have been carried out with ab initio DFT methods, however, there is very few investigation of functional dependence. Today’s Density Functional Theory approximates exchangecorrelation terms, which may cause inaccurate spin density nearby nuclei. We have done benchmark calculations to check the accuracy of various functionals for HFC of several manganeseμoxo systems. In addition, the most reliable functional for estimations of sd exchange interactions was identified. 

Molecular dynamical simulations of helium atom interacting with the XUV field aimed at predicting partial ionization yields of helium ion in various electronic states 
Petra Ruth KapralovaZdanska^{1,2} and Jan Smydke^{1,2}
^{1} J. Heyrovsky Instritute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejskova 3, 182 23 Prague 8, Czech Republic
^{2} Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, 182 21 Prague 8, Czech Republic 
This conference paper is devoted to the theoretical method which we developed for simulating ionization of the helium atom interacting with a strong electromagnetic field, with a view to later application to other atoms. It consists of two parts. The first part represents the solution of stationary Schroedinger equation for the complex scaled Hamiltonian of the helium atom. Here we focus on choosing the appropriate electronic basis set that allows for obtaining a large scale helium spectrum, which provides a sufficient density of the discretized continuum states, includes the doubly excited Rydberg states, etc. The spectrum is used in the second, dynamical part of the computational method as a part of the basis set for the timedependent wavefunction, see below. Timedependent coefficients of basis functions represent a source of information on the populations of various excited states of the helium atom. Partial sums of the populations of continuum states in each ionization threshold provide the required partial ionization yields associated with direct ionization. Except for the direct ionization, we calculate the ionization, which emerges from resonances that are populated in the process.
Details for the dynamical method are as follows: The interaction Hamiltonian is given in the classical dipole approximation. A typical pulse length is the order of fs to ps and a wavelength of 50 nm. The dynamical process is considered to be mostly adiabatic, in the sense that only one Floquet state is predominantly populated, namely, the one that corresponds to the initial electronic state of helium at zero field strength. Nevertheless, it is necessary to include nonadiabatic processes for calculating the populations of states with a long lifetime (whether they are lowlying continuum states, which are indeed rotated into the complex plane due to complex scaling, but their imaginary components are still small, or just the longlived resonances), where the adiabatic dynamics always inherently leads to their artificial deletion from the wavefunction at the end of the pulse, where the Floquet state goes back to the net initial state. Using the instantaneous Floquet states as a basis set for the timedependent wave function is still advantageous as it ensures an effective separation of the fast timedependence (due to field oscillation) and slow timedependence (due to intensity modulation). Floquet states themselves are given in the basis of the dressed states defined by the direct product of photon states and the field free states of the helium atom. 

Quantum decoherence at the femtosecond level in liquids and solids observed in neutron Compton scattering 
Erik B. Karlsson
Dept. of Physics and Astronomy
Uppsala University
Box 516
SE 75120 Uppsala
Sweden 
About 10 years ago it was found that neutron scattering on hydrogen showed anomalously low crosssections in many materials when it was observed under Compton scattering conditions (i.e. with neutron energies larger than 10 eV, where the duration of the scattering process falls in the τ_{sc} = 10^{16} – 10^{15} s range). The anomalies decreased with the neutron energy, which meant that the crosssections approached normal values for long scattering times.
This phenomenon is interpreted here as due to an entanglement between the protons (because of their indistinguishability) during the scattering process, by which certain terms in the crosssection are cancelled through the large zeropoint motion of the protons. The anomalies disappear gradually as the proton states decohere in contact with the local environment. Fitted decoherence times range from 4 •10^{15} s for proton pairs in liquid hydrogen to 5 •10^{16} s in metal hydrides. For the proton pairs in water, the data are compared with a theoretical estimate for decoherence based on the influence of fluctuations in hydrogen bonding to nearby molecules.
The fast decoherence of locally prepared entangled states in condensed media studied here is compared with decoherence (in the 10^{6}  10^{3} s range) in objects studied in quantum optics in high vacuum, with the disapperance of the superposition state in NH3 or ND3 molecules in dilute gases, and with the lifetime of superconducting qubits in solids (10^{9 s}) at low temperature.


Timedependent multiconfiguration wave function theory for molecular systems composed of two kinds of Fermi particles: Application to diatomiclike molecules 
Tsuyoshi Kato and Kaoru Yamanouchi
Department of Chemistry, School of Science, The University of Tokyo, Japan 
We propose multiconfiguration wave function theory for molecular systems composed of two kinds of Fermi particles, e.g., electrons and protons, and two heavy nuclei to describe molecular dynamics in intense laser fields. For practical applications of the theory we reduce the dimension of the consitituent orbital functions from 3D to 2D. To that end we make use of "diatomiclike molecular picture" for molecules such as CH_{3}OH, C_{2}H_{2}, and CH_{2}CH_{2}.
First, we calculate the electroprotonic ground state wave function of CH_{3}OH within the fixed nuclear model in which C and O atoms are fixed in space. By analyzing the conditional probability density functions for the protonic system, which are calculated by using the 2nd order reduced density matrix for the protonic structure, we examine the positional correlations of four protons. We find that the positional correlations are close to those in the optimized geometrical structure obtained by the standard BornOppenheimer approach, which assures applicability of our present nonBorn Oppenheimer approach.
Another example includes the calculation of the CIvectors that are newly introduced in our theory to elucidate the physical meaning of the CIvectors. From the analysis of the electrovibrational ground state wave function of 1D hydrogen molecule, we find that the effects of nonadiabatic couplings between adiabatic electronic states in the BornOppenheimer picture are properly described in the present method as the variations of the CIvectors.


Ab initio and density functional calculation of calcium binding sphingomyelin lipid molecules: A pin holder model approach 
Hiroyuki Kawabe^{1} and Kimikazu Sugimori^{2}
^{1}Department of Social Work, Faculty of Social Work, Kinjo University, Japan
^{2}Department of Physical Therapy, Faculty of Health Sciences, Kinjo University, Japan 
One of the phospholipids, sphingomyelin (SM, Nacylsphingosine1phosphorylcholine) is the most abundant component of mammalian membranes in brain and nervous tissues. It plays an important role for apoptosis, aging, signal transduction with cations. Recently, Yappert and coworkers have shown that human lens sphingomyelin and its hydrogenated derivative, dihydrosphingomyelin (DHSM) are interacted with Ca^{2+} ions to develop human cataracts [1,2]. Previously we have investigated conformational differences between an isolated SM / DHSM molecule and Ca^{2+} coordinated form by using density functional theory (DFT) which B3LYP functional and 631G(d,p) doublezeta splitvalence basis set is applied for geometry optimization and normal mode analysis. As a result, one of conformers of SMs has hydrogen bonding between hydroxyl group and phosphate group, whereas another conformer has hydrogen bonding between hydroxyl and phosphate amide group [3]. Moreover, ^{31}PNuclear Magnetic Resonance (NMR) shielding constants of the obtained conformers are investigated by using ab initio and DFT with gauge invariant atomic orbitals (NMRGIAO) calculations [4].
In this study, we apply previous results to dimer and trimer model of lipid molecules with Ca^{2+} and water molecules by quantum chemical calculations. We assume that tails of the lipids arbitrary fixed specific length in plasma membrane, like pin holder. Except for fixed tail groups, all of molecular structure of head group and solvated Ca^{2+} are fully optimized. We analyze potential energy surface (PES) with the fixed parameters that are length between tails of lipid and coordinate of Ca^{2+} approaching from outer region to phosphate.
References
[1] M. Rujoi, D. Borchman, D. B. Dupré, and M. C. Yappert, Biophys. J. 82 (2002) 30963104.
[2] M. C. Yappert and D. Borchman, Chem. Phys. Lipids 129 (2004) 120.
[3] K. Sugimori, H. Kawabe, H. Nagao and K. Nishikawa, Int. J. Quantum Chem. 108, 29352942 (2008). doi:10.1002/qua.21858
[4] K. Sugimori, H. Kawabe, H. Nagao, and K. Nishikawa, Int. J. Quantum Chem., 109 (2009) 36853693. doi:10.1002/qua.22404


Structural analysis of ligand binding mechanism of Hsp90 
Kazutomo Kawaguchi, Acep Purqon, Hiroaki Saito, Hidemi Nagao
Institute of Science and Engineering, Kanazawa University, Kanazawa 9201192 Japan 
Hsp90 is one of the molecular chaperones which protect their client proteins in the folding processes. Hsp90 usually forms a dimer and undergoes large conformational changes during its functional cycle. Binding and hydrolysis of ATP to ADP are required for these conformational changes. We performed molecular dynamics simulation of Hsp90 with ADP to elucidate molecular mechanisms of ligand binding process. The results of structural analysis of ligand binding process of Hsp90 will be presented and discussed through recent calculations. 

Blackbody, synchrotron radiation, bremsstrahlung and plasmon analyzed by Tsallis nonextensive entropy 
Jun Kawai, Abbas Alshehabi, Hiroyuki Iwasaki, Koretaka Yuge, Ágnes Nagy*
Kyoto University, Department of Materials Science and Engineering,
Sakyoku, Kyoto 6068501, Japan
*Debrecen University, H4010 Debrecen, Hungary

Manne Siegbahn once wrote that “the curve (bremsstrahlung from Xray tube) rises abruptly on the short wavelength side. In this respect the curve differs fundamentally from the curve for the radiation of a ‘black’ body, though otherwise the curves have an external resemblance”[1]. Blackbody and bremsstrahlung or synchrotron radiation are similar in their overall spectral shape but a minor difference exists [24]. The Planck’s blackbody equation is expressed through the Tsallis nonextensive entropy [5]: N(E)=1/[(1+(q1)x)^{1/(q1)}1], where N is the number of photons, x=E/kT, and q the Tsallis parameter [6,7]. When q>1 , the above equation becomes Plank’s blackbody equation. We have fitted Eqn.(1) to a synchrotron radiation (relativistic bremsstrahlung) and when q=1.05 the agreement is best and satisfactory as shown in Fig. 1. The parameter q >1 means the longrange correlation due to nonextensitivity. The blackbody is ideal gas of photons without interaction, but the photons are weakly interacting each other for the synchrotron radiation.
Similarly the plasmon energy loss peaks when Si is irradiated by e.g., 1500 eV electron beam, decays exponentially from the 1st loss to the higher orders. The deviation from the exponential decay is also expressed by the Tsallis q parameter, which indicate the intrinsic and extrinsic paths of the plasmon energy loss processes.
exp(E/kT)appears in physical chemistry, and the deviation from exponential could be interpreted by the long range interaction through the Tsallis parameter q.
References
[1] M. Siegbahn, “The Spectroscopy of XRays”, transl. G. A. Lindsay, Oxford Univ. Press, London, 1925, p. 206.
[2] J. Kawai, H. Ishii, Spectrochim. Acta, Part B, 60, 1586 (2005).
[3] J. Kawai, H. Ishii, Radiation Phys. Chem., 75, 1716 (2006).
[4] T. Tanigaki, J. Kawai, XRay Spectrom., 36, 321 (2007).
[5] C. Tsallis, Introduction to Nonextensive Statistical Mechanics, Springer (2009).
[6] Q. A. Wang, A. Le Mehaute, Phys. Lett. A, 242, 301 (1998).
[7] S. Martnez, F. Pennini, A. Plastino, C. J. Tessone, Physica A, 309, 85 (2002).


Figure 1. Comparison of synchrotron radiation (dotted)and blackbody radiation (solid line) with q=1.05.

Figure 2. Plasmon energy loss spectra.



Calculation of magnetic constants D in ZeroField Splitting by ab initio methods 
Takashi Kawakami, Keiji Kinoshita, Akira Ito, Yasutaka Kitagawa, Shusuke Yamanaka, Kizashi Yamaguchi, Mitsutaka Okumura
Graduate School of Science, Osaka University, Japan 
For theoretical treatments of ZFS parameters, previously Pederson and coworkers have developed a method calculating the ZFS parameters with the DFT methods. In the series of our studies, we developed new ab initio MO program package ("Q" by Ryo Takeda in our group). The Pederson's treatments are also included in this program. Thus, several ab initio MO methods can be applied to calculating zerofield splitting parameters caused by mainly spinorbit coupling. We examine the behavior and tendency of the method by applying it to some basic molecules such as small molecules (ex. carbene), pure organic molecular magnets, singlemolecular magnets (SMM), etc. It shows the method has good accuracy. We suggest applicable region of the method.
In addition, Neese has also developed another calculation scheme with coupledperturbed equation. This method is involved in their program package "ORCA". Thus, we also evaluated ZFS parameters by Neese's methods.


Free energy of cellpenetrating peptide in lipid bilayer membrane: coarsegrained simulation 
Shuhei Kawamoto^{1}, Takeshi Miyakawa^{2}, Masako Takasu^{2}, Ryota Morikawa^{2}, Tatsuki Oda^{1}, Hiroaki Saito^{1}, Shiroh Futaki^{3} and Hidemi Nagao^{1}
^{1}Graduate School of Natural Science and Technology, Kanazawa University
^{2}School of Life Sciences, Tokyo University of Pharmacy and Life Sciences
^{3}Institute for Chemical Research, Kyoto University

Cellpenetrating peptides (CPPs) can permeate plasma membrane [1], and are useful for delivery of drugs and transfection of DNA. Free energy ΔG to insert a molecule into lipid bilayer membrane is important to investigate the permeability of the molecule through the membrane. ΔG of small molecules, such as water and oxygen, are obtained by allatom simulations [2] with cavity insertion method. However, large molecules, such as CPP, are difficult to insert into the cavity in lipid bilayer membrane.
We estimate ΔG of CPP by steered MD method with our coarsegrained model [3]. When there is large attractive potential between CPP and lipid heads, the CPP makes inverted micelle in the lipid bilayer membrane, and the difference of ΔG between water region and lipid bilayer region is more than 66 kBT. It suggests that the spontaneous permeation of CPPs needs large driving force to overcome the barrier.
[1] I. Nakase, T. Takeuchi, G. Tanaka, S. Futaki, Adv. Drug Deliv., 60, 598 (2008)
[2] K. Shinoda, W. Shinoda, T. Baba, M. Mikami, J. Chem. Phys., 121, 9648 (2004)
[3] S. Kawamoto, et al., J. Chem. Phys., 134 095103 (2011)


Origin of magnetism  Failure of Slater's perturbation theory  
Yoshiyuki Kawazoe
Institute for Materials Research, Tohoku University, Sendai, Japan 
Starting from Slater's explanation of the Hund's rule, in these 80 years origin of magnetism has been believed to be the exchange interaction between electrons in atoms, molecules, and bulk materials. His theory assumes degenerate states for kinetic and potential energies. Starting from Davidson on the excited states in He atom in 1965, several papers have been published to doubt the Slater's theory. However, unfortunately these contributions used simple HF theory and not so accurate. We have continuously made a series of accurate calculations including electron interactions fully to finalize this contradiction, since this is a very important problem to understand the origin of magnetism. To confirm our results we numerically check the virial theorem for equilibrium states; 2T+V=3P&Omega=0. This theorem requires for the total energy E=T+V to be E=V/2=T; T and V are not independent. Based on this fundamental theorem, we have completely certified that the Slater's perturbation theory violates this necessary condition, and is wrong. The origin of magnetism is not the exchange interaction, but it is mainly the interaction between positively charged nucleus and electrons with spin. Last year we extended this new finding up to the second Hund's rule, which is for the angular momentum states, as the first theoretical contribution to understand it. In my talk detailed theory and numerical results will be given, and model calculations assuming perturbation theories are categorized to be good or wrong. 

NuclearRelativistic ManyBody Perturbation Theory to Parity Nonconservation Effect in Heavy Atoms and Nuclei 
Olga Yu. Khetselius
Department of Mathematics, Odessa OSENU University, Odessa9, Ukraine 
During the past two decades, the nuclear and atomicoptical experiments to detect parity nonconservation (PNC) have progressed to the point where PNC amplitudes can be measured with accuracy on the level of a few percents in certain heavy atoms and significantly worse in some nuclei (Mossbauer spectroscopy). Nowadays the PNC in atoms has a potential to probe a new physics beyond the standard model. Promising idea (Forston) is to apply the techniques of laser cooling and ion trapping to measurement of the PNC in 6s^{2}S_{1/2}5d^{2}D_{3/2} transition of the Ba^{+}. In our paper we systematically apply the nuclearrelativistic manybody perturbation theory formalism [1] to precise studying PNC effect in heavy atoms with account for nuclear, correlation and QED corrections. There are determined the PNC radiative amplitudes for a set of nuclei (atoms): 133Cs, 137Ba^{+}, 173Yb with account of the exchangecorrelation, Breit, weak ee interactions, QED and nuclear (magnetic moment distribution, finite size, neutron skin) corrections, nuclearspin dependent corrections due to anapole moment, Zboson [(A_{n}V_{e}) current] exchange, hyperfineZ exchange [(V_{n}A_{e}) current]. The weak charge is found for 133Cs, 205Tl and 173Yb and comparison with Standard Model is done. Using the experimental value (E_{PNC}/b)= 39mV/cm (Tsigutkin et al, 2009) and our calculated amplitude value 9.707*10^{10} iea_{B}one could find for 173Yb (Z=70, N=103) the weak charge value Q_{W}=92.31 (the SM gives Q_{W}=95.44). The received data are compared with known earlier and recent results [1,2]. The role of the nuclear effects contribution (corepolarization contributions, which are induced by valent protons of a nucleus), spatial distribution of magnetization in a nucleus (the BohrWeisskopf effect), neutron skin correction and the nonaccounted high order QED corrections are analyzed.
References
[1] O.Khetselius, Phys.Scripta T34, 014023 (2009); Int.J.Quant.Chem. 109, 3330 (2009); A.V.Glushkov, O.Khetselius etal, Frontiers in Quantum Systems in Chem. and Phys. (Springer) 18, 505 (2008).
[2] W. Johnson, M.S.Safronova, U.I.Safronova, Phys.Rev. A69, 062106 (2003); V.V.Flambaum, J.S.Ginges, Phys.Rev. A72, 052115 (2005).


Electric field polarization in conventional Density Functional Theory:
from quasilinear to 2D and 3D extended systems 
Bernard Kirtman,^{1}, Valentina Lacivita^{2}, Roberto Dovesi^{2} and Heribert Reis^{3}
^{1}Department of Chemistry and Biochemistry, University of California, Santa Barbara, USA
^{2}Departimento di Chimica IFM, Universitá di Torino, Italy
^{3}The National Hellenic Resarch Foundation, Athens, Greece 
About a dozen years ago it was observed that KohnSham density functional theory leads to a catastrophic overshoot of the static electronic polarizability and hyperpolarizability when these properties are determined for polyacetylene chains of increasing length using conventional exchangecorrelation functionals. Since then the overpolarization in DFT calculations has been demonstrated for a wide variety of conjugated systems including prototypical molecular hydrogen chains with different intra and intermolecular distances. Although longrange corrected functionals may mitigate this effect to some extent, it is not clear that they systematically improve upon the HartreeFock approximation.
Meanwhile there has been no corresponding investigation of the DFT overshoot for 2D and 3D systems. A first study for (i) molecular hydrogen chains in 2D/3D geometries, (ii) the prototype LiF ionic system, and (iii) polycyclic aromatic coronenetype structures will be presented. Contrary to prediction, the overshoot in 1D for molecular hydrogen chains persists in 2D and 3D. A natural population analysis shows that this is due to fieldinduced intermolecular charge transfer leading to a buildup of negative/positive charge at the 1D chain ends, which is essentially undamped in higher dimensions. The same situation occurs in LiF, although the degree of overpolarization is reduced in this ionic system. For (iii) the analysis involves comparison with the linear acenes and is not as straightforward. Nonetheless, a 2D overshoot is definitely indicated, although it may be somewhat damped. Finally, we confirm that the fullerenes are truly 0D in the sense that they do not show any overshoot. 

Computational study of conformational preferences in intermediates and transition states of the hydrolysis of dimethyl phosphate 
Makoto Kita,^{1} Haruki Nakamura^{1} and Yu Takano^{1}
^{1}Institute for Protein Research, Osaka University, Japan

Phosphate diester is a basic structure in DNA and RNA. Hydrolysis mechanism of phosphate diester is important for understanding decomposition reaction of nucleic acid.
In this study, we have explored the hydrolysis reaction pathway of dimethyl phosphate, which is the simplest phosphate diester, with two nucleophiles (hydroxide and water), using the density functional theory (B3LYP/6311++G(2d,2p)) with PCM (polarizablecontinuum model). Since it was reported that the conformations of intermediates and transition states influence the reaction mechanism of transacylation of methyl acetate with methoxide [1], we focused on the conformational preferences in the hydrolysis reaction. The computed reaction pathway was confirmed by IRC (intrinsic reaction coordinate) calculation.
In hydrolysis of dimethyl phosphate with hydroxide, a concerted reaction pathway was obtained in the gas phase, whereas a stepwise reaction pathway was obtained in the aqueous phase. In the gas phase, the conformation of the transition state was different from that of the earlier study [2], but the reaction mechanism was similar to each other. The conformations hardly influence the energetics of the gasphase hydrolysis of dimethyl phosphate. On the other hand, in the aqueous phase, the reaction pathway and the activation and reaction energies were very different from those of the earlier study [2], due to the differences in the computational procedure.
We have also explored the reaction mechanism of the hydrolysis of dimethyl phosphate with water. In the gas phase, the most stable conformation of the reactant (conf1) changed to the other conformation (conf2). The reaction proceeded with conf2, and the stepwise reaction pathway was obtained. This is because the activation energy of the hydrolysis of conf2 is lower than that of conf1, and because the activation energy of conformational change from conf1 to conf2 is as low as 2.2 kcal/mol. In the aqueous phase, the proton transfer, the first step of hydrolysis, did not occur, implying that the hydrolysis occurs by a proton shuttle mechanism.
References
[1] Takano, Y.; Houk, N. K. J. Phys. Chem. A 2004, 108(52), 1174011751.
[2] Ribeiro, J. M. A.; Ramos, J. M.; Fernandes, A. P. J. Chem. Theory Comput. 2010, 6(8), 22812292.


Twolayer QM/QM’ calculations for a geometry optimization of large biradical systems 
Yasutaka Kitagawa, Toru Saito, Yusuke Kataoka, Natsumi Yasuda, Hiroshi Hatake,
Toru Matsui, Takashi Kawakami, Shusuke Yamanaka, Mitsutaka Okumura, Kizashi Yamaguch
Graduate School of Science, Osaka University, Japan 
With the recent progress in quantum chemistry, we can calculate electronic structures, energies and energy derivatives of large molecules by the first principle methods. A brokensymmetry (BS) (or an unrestricted: U) method approximately but easily corrects the static correlation at the lower computational costs. However the BS method involves a serious problem called a spin contamination error (SCE). For the problem, our group has proposed a spinprojection method to eliminate the SCE from the energy derivatives based on Yamaguchi’s approximate spin projection (AP) procedure [14]. By the AP method, one can optimize the geometry of the biradical systems without SCE at the costs of the BS level calculations. However one must carry out 6N (N = optimizing atoms) times singlepoint calculations previous to the geometry optimization because it uses a numerical derivative for d<S2>/d R values. In addition, it also requires both the lowspin and the highspin state calculations during the geometry optimization. Therefore the reduction of the computational costs is a problem of the AP method for the optimization of the larger biradical systems such as a binuclear metal complex. In this study, we attempt to combine the AP method and the spinrestricted (R) methods, i.e. twolayer QM/QM’ approach based on ONIOM method. In the method, the effect of the outerligands is included by the restricted method whilst an energy gradient of the core is calculated by the AP method using a reduced (small) model. The detail about the method and results are illustrated in the presentation.
References
[1] Y. Kitagawa, T. Saito, M. Ito, M. Shoji, K. Koizumi, S. Yamanaka, T. Kawakami, M. Okumura, K. Yamaguchi, Chem. Phys. Lett. 2007, 442], 445.
[2] T. Saito, Y. Kitagawa, M. Shoji, Y. Nakanishi, M. Ito, T. Kawakami, M. Okumura, K. Yamaguchi, {it\ Chem. Phys. Lett. 2008, 456, 76.
[3] T. Saito, S. Nishihara, Y. Kataoka, Y. Nakanishi, T. Matsui, Y. Kitagawa, T. Kawakami, M. Okumura, K. Yamaguchi, Chem. Phys. Lett., 2009, 483, 168.
[4] Y. Kitagawa, T. Saito, Y. Nakanishi, Y. Kataoka, T. Matsui, T. Kawakami, M. Okumura, K. Yamaguchi, J. Phys. Chem. A., 2009, 113, 15041. 

The band 12 issue of norbornane: a comparison between symmetry adapted cluster expansion configuration interaction (SACCI) and the third order algebraic diagrammatic construction scheme [ADC(3)] 
S. Knippenberg^{1} and B. Hajgató
^{1} Service de Chimie des Matériaux Nouveaux, Université de Mons, Place du Parc 20, B7000 Mons, Belgium
^{2} Eenheid Algemene Chemie, Vrije Universiteit Brussel (VUB), Faculteit Wetenschappen, Pleinlaan 2, 1050 Brussels, Belgium 
In line with a recent study of the electronic structure of the cage compound norbornane [1, 2], symmetry adapted cluster expansion configuration interaction (SACCI) general R calculations have been performed and compared with results obtained by the third order algebraic diagrammatic construction scheme [ADC(3)]. Comparison has been made with previously performed electron momentum spectroscopy (EMS) and ultra violet photoelectron measurements. The region around 25 eV (band 12), characterized by an elaborated band in the EMS spectrum which is missing in previous Green's function and ADC calculations, is investigated. This study is completed with outervalence Green's function (OVGF) and SACCI/SDR calculations. Since ADC(3) only includes 2h1p shakeup states, while SACCI generalR also includes higher order ones, the agreement between both methods assures that the higher order shakeup states do not play an important role in the ionization spectra of norbornane. The band12 issue of norbornane is therefore still open, while a tentative description in terms of ultrafast nuclear dynamical effects and autoionization processes has become more plausible.
[1] S. Knippenberg, K. L. Nixon, M. J. Brunger, T. Maddern, L. Campbell, N. Trout, F. Wang, W. R. Newell, M. S. Deleuze, J.P. François, D. A. Winkler, J. Chem. Phys. 121 (2004), 10525.
[2] S. Knippenberg, M. S. Deleuze, T. J. Cleij, J.P. François, L. S. Cederbaum, J. H. D. Eland, J. Phys. Chem. A 109 (2005), 4267.


Analysis for constructing protein nanofiber including metal ions

Yu Komatsu,^{1} Shuhei Kawamoto,^{2} Takeshi Miyakawa,^{1} Ryota Morikawa,^{1} Masako Takasu,^{1} Satoshi Akanuma^{1} and Akihiko Yamagishi^{1}
^{1}School of Life Sciences, Tokyo University of Pharmacy and Life Sciences, Japan
^{2}Graduate School of Natural Science & Technology, Kanazawa University, Japan 
As materials used in nanotechnology, proteins can be applied to many fields. Our aim is to fabricate a nanofiber using arbitrary proteins as maintaining their native structures. By inducing mutations in the adaptor proteins, hydrophobic and electrostatic interaction can be modified. By means of mixing the two proteins, the fiber may be organized spontaneously. As the materials of nanofiber formation, we are testing three proteins: LARFH, Sulerythrin and IPMDH.
In this research, we analyzed the three proteins which are candidates for constructing a nanofiber and investigated conditions that show high stability using molecular dynamics (MD). Sulerythrin contains two pairs of Zn^{2}+ and Fe^{2+}. We perform quantum calculation to investigate how these ions affect the stability as a fiber by quantum computing. Moreover, we perform umbrella sampling simulations to obtain PMF (Potential of Mean Force), from which binding energy Δ G_{bind} is calculated.
References
［1］S. Akanuma et al., J. Biochem, 147, 371 (2010)
［2］J. A. Lemkul et al., J. Phys. Chem. B, 114, 1652 (2010)


Quantum calculations on transient species in physics and chemistry

Najia Komiha
LCTM University Mohamed VAgdal
Rabat Morocco 
Informations on transient species are often necessary to explain formation, dissociation or spectroscopic properties of molecules. The quantum chemistry method used should be able to discribe these species. The case of transition states in organic chemistry is presented here. As an example, The reactional mechanism of the 1,3 dipolar cycloaddition of a cyclic nitrone on a substituted enoate is studied using the DFT method.This method take into account a aprt of the correlation energy and gives qualitative results . Structures of eight possible cycloadducts and transition states are determined. Relative rates , stereo and regioselectivity is analysed and discussed.
The excited electronic states are also transient species of great spectroscopic interest .S_{2}O is a molecule of atmospheric medium.Its formation (or dissociation) at low energy is studied here. The Potential Energy Surfaces (PES) of all states correlating to the lowest asymptote are mapped using the highly correlated method MRCI+Q. The spinorbit coupling is taken into account. One dimensional cuts of the threedimensional potential energy surfaces are presented for linear and bent geometries. Anisotropy in regard of the different approaches is shown and the SSO one seem to be favored.
A study of the sulfur chromophors are then presented and electronic excited states responsible of color of S_{3}^{}, S_{4}^{}, S_{4}^{+} determined The PES and some spectroscopic constants of the lowest states of S_{3}^{} are mapped using The SACASSCF and CCSD(T) accurate methods.
References
1) ‘Theoretical study of the mechanism of the 1,3dipolar cycloaddition reaction of methyl3fluoro3trifluoromethyl prop2Enoate with Pyrroline1Oxyde’
K. Marakchi, H. Abou El Makarim, O. K. Kabbaj, N. Komiha
Phys. Chem. News 52 (2010) 128136
2) ‘On the formation of S2O at low energies: An AbInitio study’
Isabelle Navizet, Najia Komiha , Roberto Linguerri, Gilberte Chambaud and Pavel Rosmus
Chemical Physics Letters, Volume 500, Issues 46, 19 November 2010, Pages 207210
3) ‘Electronic states of the Ultramarine chromophore S3‘
R.Linguerri,N.Komiha,J.Fabian,P.Rosmus
Z.Phys.chem.,222(1),2008,163176


Control of Vibrational Dynamics and Reaction of C_{60} and Its Derivatives by Nearinfrared Fields 
Hirohiko Kono,^{1} Naoyuki Niitsu,^{1} Kaoru Yamazaki,^{1} Katsunori Nakai,^{2} Mikito Toda,^{3} and Stephan Irle^{4}
^{1}Department of Chemsitry, Graduate School of Science, Tohoku University, Sendai 9808578, Japan.
^{2}Department of Chemistry, School of Science, The University of Tokyo, Tokyo 1130033, Japan.
^{3}Department of Physics, Faculty of Science, Nara Women's University, Nara 6308506, Japan.
^{4}Department of Chemistry, Graduate School of Science, Nagoya University, Nagoya 4648601, Japan 
We developed the timedependent (TD) adiabatic state approach to investigate the electronic and nuclear dynamics of polyatomic molecules in intense laser fields, where the total wave function is expanded in terms of TD adiabatic states defined as the eigenfunctions of the "instantaneous" electronic Hamiltonian including the dipole interaction with a laser field [1]. Nuclear dynamics of a molecule in a nearinfrared (IR) field can be described by classical molecular dynamics on TD potentials. By using this approach combined with ab initio electronic structure calculations, we investigated the dynamics of C_{60} interacting with intense IR pulses and found that largeamplitude vibration with energy of > 20 eV is induced mainly in the oblateprolate h_{g}(1) mode of C_{60} and its cations [2]. We also demonstrated that largeamplitude vibration of the h_{g}(1) mode persists for 25 ps. This means that mode selectivity is achieved by adjusting the intervals between pulses in a pulse train. We then investigated the fragmentation dynamics of C_{60} on the ns time scale by using a DFTB method. It is confirmed that the main process is C_{2}elimination after StoneWales (SW) rearrangements due to rapid vibrational energy migration in the carbon network. A SW rearrangement occurs within 100 fs only when a sufficient energy to go over the transition state is localized in a C=C bond and its surrounding C atoms and the induced motion fits the direction of the transition state. This suggests the controllability of this local rearrangement leading to the optimization of branching ratios of fragments, though fragmentation in the ns range is considered "statistical." We have also investigated the fieldinduced dynamics of polyhydroxy fullerenes by using the DFTB method and found that hydroxy groups migrate rapidly in the carbon netowork and water molecules are ejected from the parent molecule. These processes are considered key steps for the transformation of polyhydroxy fullerenes into singlewalled nanotubes, multiwalled nanotubes and carbon onions [3].
[1] Y. Sato, H. Kono, S. Koseki and Y. Fujimura, J. Am. Chem. Soc. 125, 8019(2003).
[2] K. Nakai, H. Kono, Y. Sato, N. Niitsu, R. Sahnoun, M. Tanaka and Y. Fujimura, Chem. Phys. 338, 127(2007).
[3] V. Krishna, N. Stevens, B. Koopman and B. Moudgil, Nature Nanotech. 5, 330(2010). 

Functional Features of Voids of Nanosized Golden Fullerenes 
Eugene S. Kryachko
Bogolyubov Institute for Theoretical Physics, Kiev, 03680 Ukraine
Email: eugene.kryachko@ulg.ac.be

Generally speaking, an arbitrary 3D molecular structure is either spacefilled, compact, without any void, or possesses some void(s) or emptiness that result in a hollow cage shape. Fullerenes, such as the buckyball C_{60}, belong to the latter category. Similar fullerenelike structures or hollow cages have been recently discovered for other chemical elements, among which gold is a particular one – definitely, `noblesse oblige' works out – due to its rather unique properties mostly dictated by strong relativistic effects.
When one molecule interacts with another, their outer space between them is patterned by chemical bonds. In this sense, hollow molecular cages are distinguishably different. If a void of an arbitrary fullerene is of a sufficient size, it enables to form chemical
bond(s) in the interior, void space with guest atoms, ions or molecules which are trapped inside, encapsulated or confined within void. This results in the formation of so called ‘endohedral’ or @fullerenes which are manifest in a variety of remarkable features. Therefore, by the definition, molecular hollow cages possess atoms that are capable, on the one hand, to form chemical bonds with molecules from the outer space and on the other, from the inner, void one. This implies a bifunctionality of the chemical reactivity of such molecular systems  the outer or exoreactivity, on the one hand, and the inner, void, or endoreactivity on the other.
The present work further pursues the theme of the void molecular reactivity [1,2] and investigates the functional features of void reactivity of nanosized golden fullerenes Au32 and higher by invoking, instead of the global characteristics, such as the ionization energy and electron affinity, which traditionally characterize chemical reactivity, the local ones: the molecular electrostatic potential, HOMOLUMO patterns, and atomic and ionic probing species. The formation of the chemical bonding patters are studied for some encaged atoms and diatoms, and compared with the analogous endohedral C_{60}fullerenes. A surprising confinement propensity of the 3D spacefilled cluster Au_{20}( T_{d}) is under consideration as well.
\vspace{0.25
1. E. S. Kryachko and F. Remacle. J. Phys.: Conf. Series 248, 012026 (2010).\\
2. E. S. Kryachko and F. Remacle. In Advances in the Theory of Quantum Systems in Chemistry and Physics. Ed. by P. Hoggan, J. Maruani, P. Piecuch, G. DelgadoBarrio, and E. J. Brändas. Springer, Berlin, 2011. Vol. B22.


General Coalescence Conditions for the Exact Wave Functions 
Yusaku I. Kurokawa, Hiroyuki Nakashima, and Hiroshi Nakatsuji
Quantum Chemistry Research Institute, JST, CREST, Kyodai Katsura Venture Plaza 106, Goryo Oohara 136, Nishikyoku, Kyoto 6158245, Japan 
We derived necessary conditions for exact wave functions of the timeindependent Schrödinger equation that must be satisfied at a coalescence (or cusp) region. Some of such conditions are already known as the Kato's cusp conditions (CC) [1] and Rassolov and Chipman's CC [2]. In this study, we have generalized them to be relations among higher order derivatives of wave functions. Furthermore, we have extended them to be applicable not only to the Coulombic system but also to any systems where the interaction between two particles is represented in power series of interparticle distance. We named these conditions to be General Coalescence Conditions (GCCs). Any wave functions must satisfy GCCs; otherwise they never become exact. The Kato's CC and Rassolov and Chipman's CC are included in GCCs as special cases.
We applied the Free Complement (FC) wave functions [3] (which is nearly exact) of the hydrogen atom in the ground and excited states, the harmonic oscillator, a system with interacting potential of V = r, and the helium atom to GCCs and confirmed that the FC wave functions satisfy GCCs.
[1] T. Kato, Commun. Pure Appl. Math. 10, 151 (1957).
[2] V. A. Rassolov and D. M. Chipman, J. Chem. Phys. 104 (24), 9908 (1996).
[3] H. Nakatsuji, Phys. Rev. Lett. 93 (3), 030403 (2004); H. Nakatsuji, Phys. Rev. A 72 (6), 062110 (2005).


Experimental investigations of single photon multiple ionization
two examples : formation of HBr^{3+} and of double core holes

P Lablanquie
LCPMR, CNRS and University ParisVI
75231 Paris Cedex 05
FRANCE 
Our current research focuses on the experimental investigation of multiple ionization process as induced by single photon interaction. Its first interest is that it results from electron correlations, and can be used to probe them, the second interest is that it gives access to multiply charged species whose properties can be explored in fine detail. We will present two examples from our recent investigations:
1) HBr^{3+} species have been formed by double Auger decay of the Br 3d hole [1] Direct and cascade emission of the 2 Auger electrons are used to probe the lower HBr^{3+} potential curves. They are purely dissociative to H^{+} + Br^{2+} limits, but present a peculiar topology due to the residual H + Br^{3+} binding, as confirmed in our ab initio calculations. [1]
2) Double core holes have been produced by single photon double ionization. The two Kshell holes can be produced either on the same atom [2] or on neighboring atoms inside the molecule. We will discuss the probabilities for these double ionization paths, and the properties (spectroscopy, Auger decays) of the resulting double core hole states.
[1]. F. Penent et al., Phys. Rev. Lett. 106, 103002 (2011).
[2]. P. Lablanquie et al., Phys. Rev. Lett. 106, 063003 (2011).


New coupled cluster methods for bondbreaking potential energy surfaces 
Shuhua Li, Jun Shen, Enhua Xu, Zhuangfei Kou
School of Chemistry and Chemical Engineering, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, Institute of Theoretical and Computational Chemistry, Nanjing University, Nanjing, 210093, P. R. China. shuhua@nju.edu.cn

In this talk, I will present our recent advances in coupled cluster methods for treating bondbreaking potential energy surfaces. The first approach is the coupled cluster singles, doubles with partial triples and quadruples based on the unrestricted HartreeFock (UHF) reference [1]. In this approach, canonical UHF molecular orbitals are first transformed into corresponding orbitals so that each spin orbital is paired with only one spin orbital. The method computationally scales as the seventh power of the system size. Test applications demonstrate that this method provides much more accurate descriptions for singlebond breaking processes than the UHFbased CCSD(T) method. Another approach is an approximate coupled cluster singles and doubles, with a hybrid treatment of triple excitations [denoted as CCSD(T)h] [2，3]. With the concept of active and inactive corresponding orbitals (occupied or virtual), triple excitations can be divided into two subsets: (1) “active” triples involving at least one occupied active orbital and one virtual active orbital and (2) the remaining triples. The amplitudes of these two classes of triple excitations are obtained via two different approaches. The present method has been applied to study the bondbreaking potential energy surfaces in a number of small molecules. For all systems under study, the overall performance of CCSD(T)h is very competitive with that of CCSDT, and much better than that of the UHFbased CCSD(T).
References:
[1] E. Xu, J. Shen, Z. Kou, S. Li J. Chem. Phys. 132, 134110 (2010).
[2] J. Shen, E. Xu, Z. Kou, S. Li J. Chem. Phys. 132, 114115 (2010).
[3] J. Shen, E. Xu, Z. Kou, S. Li J. Chem. Phys. revised, 2010.


Theoretical Treatments of Ultrafast Nonadiabatic Processes by the Density Matrix Method 
Y. L. Niu^{1} C. K. Lin^{1} C. Y. Zhu^{1} Y. Fujimura^{1} M. Hayashi^{2} and Sheng Hsien Lin^{1}
^{1}Department of Applied Chemistry, Institute of Molecular Science and Center for Interdisciplinary Molecular Science, National ChiaoTung University, Hsinchu Taiwan
^{2}Center for Condensed Matter Sciences, National Taiwan University, Taipei Taiwan

Using femtosecond timeresolved experiments to study ultrafast processes, quantum beat is often observed. To analyze the fs timeresolved spectra, the density matrix method which can take care of the description of the dynamics of population and coherence of the system is a powerful theoretical technique. In this talk, the π π*  n π* transition of pyrazine will be used as an example to demonstrate the application of the density matrix method. Recently, Suzuki’s group have employed the 22 fs laser to study the dynamics of the n π* state of pyrazine. In this case, conical intersection is commonly believed to play an important role in this nonadiabatic process. How to treat the effect of conical intersection on nonadiabatic processes and fs timeresolved spectra will be presented.


The Chemistry of Bioluminescence: An Analysis of Chemical Functionalities 
Isabelle Navizet^{1}, YaJun Liu^{2}, Nicolas Ferre^{3}, Daniel RocaSanjuan^{4}, Mickael Delcey^{4} and Roland Lindh^{4}
^{1}University of the Witwatersrand, South Africa
^{2}Beijing Normal University, China
^{3}Universités d'AixMarseille, France
^{4}Uppsala University, Sweden 
Firefly luciferase is one of the most studied bioluminescent system. It has been extensively studied both theoretically and experimentally. Based on these studies we will herein give a review on the current understanding of the bioluminescent process from a chemical functionality perspective. This presentation will emphasize three key components: the chemiluminophore, the electrondonating fragment and how these are affected by the substrateenzyme interaction. The understanding is based on details of how the peroxide OO bond supports the production of electronically excited products and how the Charge Transfer Induced Luminescent, CTIL, mechanism, with the aid of an electrondonating group, lowers the activation barrier, to support a reaction in living organisms. For the substrateenzyme complex it is demonstrated that the enzyme can affect the hydrogenbonding around the CTIL controlling group resulting in a mechanism for color modulation. Finally, in the light of the purpose of the fragments of the luciferinluciferase complex to provide key chemical functionalities we will analyse other luciferinluciferase systems with respect to similarities and differences.
If time available I will discuss the significance of the difference between the chemiluminescent and fluorescent states of luciferin and its implications for theoretical and experimental investigations.


Simulations of SolidState Vibrational Circular Dichroism Spectroscopy by Using Fragmentation Quantum Chemical Calculations 
Jing Ma and Nan Jiang
School of Chemistry and Chemical Engineering, Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry of MOE, Nanjing University, Nanjing, Jiangsu, 210093, People’s Republic of China 
Simulations of vibrational circular dichroism (VCD) spectroscopy of optical active aggregates of chiral molecules in the amorphous solid encounter great difficulties in the description of complicated intermolecular interactions by using the conventional quantum mechanical (QM) methods. The fragmentation approach is applied to calculate the VCD spectra of the covalently bonded oligomers and nonbonded molecular aggregates of (S)alternarlactam. Starting from the statistically averaged configurations that are sampled from the molecular dynamic simulations, the target oligomers or packing systems are divided into several fragments with a proper treatment of boundary effects on the separated segments. Each fragment is embedded in the background point charges centered on the distant atoms to simulate the longrange electrostatic interactions. The total VCD signals are assembled from the rotational strength of all the fragments. Test calculations on the bonded oligomers and molecular aggregates using fragmentation method show good agreement with the conventional QM results. The fragmentbased VCD calculations on molecular aggregates give a better agreement with experimental spectra than the Boltmannweighted spectra of various possible monomeric, dimeric, and trimeric configurations. The computational cost of fragmentation calculation scales linearly with the number of the molecular fragments, facilitating the future applications to a wide range of the largesized chiral systems. 

Exploring Multiple Potential Energy Surfaces 
Satoshi Maeda,^{1,2} Koichi Ohno^{3} and Keiji Morokuma^{2,4}
^{1}The Hakubi Center, Kyoto University, Kyoto 6068302, JAPAN
^{2}Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 6068103, JAPAN
^{3}Toyota Physical and Chemical Research Institute, Nagakute, Aichi 4801192, JAPAN
^{4}Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, GA 30322, USA 
Nonadiabatic transitions play key roles in many chemical reactions [1], including photoreactions, ionmolecule reactions, spinflip reactions, and so on. Since multiple potential energy surfaces (PESs) are involved in such reactions, one has to explore multiple PESs systematically to uncover its entire reaction mechanism. Minimum on seam of crossing (MSX) structures are often considered as critical points of nonadiabatic transitions. On each PES, chemical bond rearrangements may take place via a transition state (TS) structure. In short, one has to locate all important MSXs as well as TSs for multiple PESs.
On excited state PESs, molecules take unexpected (chemically unstable) geometries more frequently than on the ground state PES. Hence, use of an automated reaction path search method is highly recommended to locate all important TSs and MSXs systematically. However, automated exploration of excited state PESs has been very difficult because there are singular points in low energy regions of excited state PESs due to conical intersections (CIs). There has been no practical method for the automated MSX search either.
Recently, we have proposed a recipe for exploring multiple PESs by using an automated reaction path search method which has previously been applied to single PESs [2]. Although any such methods can be used in the recipe, the global reaction route mapping (GRRM) method was employed in this study [3]. By combining GRRM with the proposed recipe, all critical regions, i.e., TSs, CIs, MSXs, associated with multiple PESs can be explored automatically. In applications to photodissociation reactions of simple molecules, the present approach led to discovery of many unexpected nonadiabatic pathways, by which some complicated experimental data have been explained very clearly [4].
[1] S. Nanbu, T. Ishida, and H. Nakamura, Chem. Sci. 2010, 1, 663.
[2] S. Maeda, K. Ohno, and K. Morokuma, J. Phys. Chem. A 2009, 113, 1704.; S. Maeda, K. Ohno, and K. Morokuma, Adv. Phys. Chem. Submitted.
[3] K. Ohno and S. Maeda, Phys. Scr. 2008, 78, 058122.
[4] S. Maeda, K. Ohno, and K. Morokuma, J. Phys. Chem. Lett. 2011, 1, 1841.; R. Nádasdi, G. L. Zügner, M. Farkas, S. Dőbé, S. Maeda, and K. Morokuma, ChemPhysChem 2010, 11, 3883.; H. Xiao, S. Maeda, and K. Morokuma, J. Phys. Chem. Lett. 2011, 2, 934.


Laser ElectronGammaNuclear Spectroscopy of Diatomic and Multiatomic Molecules 
Svetlana V. Malinovskaya,^{1} and Andrey A. Svinarenko^{2}
^{1}Department of Chemistry, Odessa University, Odessa9, Ukraine
^{2}Department of Mathematics, Odessa University, Odessa9, Ukraine 
An important class of problems connected with modelling the cooperative laserelectrongammanuclear phenomena in diatomic and multiatomic molecules [1,2] is now of a great interest. It includes a calculation of the probabilities and energies of the mixed gammanuclear and optical quantum transitions in molecules, intensities of the complicated gammatransitions due to the changing of the molecular excited states because of the gamma nuclear transition. We present a consistent, quantum approach to calculation of the probabilities of the different cooperative laser electrongammanuclear processes in different molecules [2] (including the set of electron or vibrationrotational satellites of the gammanuclear spectrum). The calculation results for the electrongammanuclear transition probabilities in the diatomic (the nucleus 127I with E=203keV in molecule of H^{127}I) and vibrationnuclear transition probabilities for some threeatomic XY_{2}, fiveatomic XY_{4} molecules are given. In particular, we present the results of calculation for the vibrationnuclear transition probabilities in a case of the emission and absorption spectrum of nucleus 188Os (E=155 keV) in the molecule of OsO_{4} and nucleus 191Ir (E=82 keV) in the molecule IrO_{4}.
References:
[1]. V.S.Letokhov, V.Minogin, JETP. 69, 1369 (1975); A.Glushkov, L.Ivanov, Phys.Lett.A 170, 33 (1992); A.Glushkov, L.N.Ivanov, V.S.Letokhov, Preprint of ISAN N AS4, MoscowTroitsk, (1991);
[2]. A.Glushkov, S.Malinovskaya, O.Khetselius, Europ.Phys.Journ. T160, 195 (2009); Molec.Phys.(UK) 108, 1257 (2008); Int.J. Quant. Chem. 104, 496 (2005); Frontiers in Quantum Systems in Chem. and Phys. (Springer) 18, 523 (2008).


TGMD: Thermal Gaussian Molecular Dynamics for Quantum Dynamics
simulations of manybody systems. Application to liquid parahydrogen. 
Ionut Georgescu, Jason Deckman and Vladimir Mandelshtam
University of California at Irvine 
I will describe a novel method, the Thermal Gaussian Molecular Dynamics (TGMD), for simulating the dynamics of quantum manybody systems.
As in the Centroid Molecular Dynamics (CMD), in TGMD the Nbody quantum system is mapped to an Nbody classical system. The associated both effective Hamiltonian and effective force are computed within the Variational Gaussian Wavepacket (VGW) approximation. The TGMD is exact for the hightemperature limit, is accurate for short times and preserves the quantum canonical distribution. For a harmonic potential it provides exact time correlation functions at least for the case, when one of the two operators is a linear combination of the position and momentum operators.
While conceptually similar to CMD and other Quantum MD approaches, the great advantage of TGMD is its computational efficiency. So far the method has been applied successfully to a liquid system of up to N=2592 paraH_{2} molecules.


The Dirac equation: spin, Zitterbewegung, the Compton wavelength,
and the foundation of the electron mass 
Jean Maruani
Laboratoire de Chimie Physique  Matičre et Rayonnement
11, rue Pierre et Marie Curie  75005 Paris, France 
The Dirac equation, which was derived by combining, in a consistent manner, the relativistic invariance condition and the quantum superposition principle, has shown its fecundity by explaining the spin, predicting antimatter, and providing a consistent picture of Schrödinger's trembling motion. It has also generated two paradoxes: one is the expectation value of the electron velocity; and the other is the halfinteger value of the electron spin (which has shown agreement with all observations, including magnetism). In this paper, we discuss these paradoxes in relation with the structure and mass of the electron. 

From Koopmans to accurate estimates of molecular core ionization energies
through parameterized allometric scaling 
Jean Maruani and Christiane Bonnelle
Laboratoire de Chimie Physique  Matičre et Rayonnement
11, rue Pierre et Marie Curie  75005 Paris, France 


On the Reduced Density Matrix: in appreciation of Kodai Husimi 
Roy McWeeny
University of Pisa, Italy 
Seventy years ago Husimi introduced a new concept in the theory of Nparticle systems: his Reduced Density Matrix (RDM) enabled one to discuss the properties of the whole system in terms of probability densities referring to only n particles at a time.
For n=1, the RDM gives the "particle density" (e.g. an electron density), while for n=2 it describes the "correlation" between the motions of two particles.
In the years that followed, the RDM has become evermore important. For electronic systems in particular, it is now possible to calculate the 2electron RDM with an accuracy rivalling that of conventional (wave function) methods.
This short review touches not only the development of the methodology, but also its value in discussions of "separability", a topic that goes to the roots of quantum mechanics and continuing arguments of a philosophical nature. 

Spin Catalysis of Dioxygen Activation by Enzymes 
Boris Minaev,^{1,2} Valentina Minaeva^{1} and Hans Agren^{2}
^{1}Department of Chemistry, Bogdan Khmelnitskij National University, Cherkasy, Ukraine
^{2}Department of Theoretical Chemistry, Institute of Biotechnology, Royal Institute of Technology, Stockholm, Sweden 
In stable organic substances all electron spins are paired and molecules have the singlet ground state. In order to activate chemical transformations and cleave the chemical bond one has to produce spin uncoupling. Interaction with collision partner in bimolecular reactions of diamagnetic species usually leads to activation barrier produced by avoided crossing of the closed shell reactant state and the doublytriplet excited singlet state. In order to lower the barrier one can add new nonpaired electrons to the reacting system or induce spin flip for enhancement of the intersystem crossing to the singlyexcited triplet state. This can be done by exchange interaction with paramagnetic transition metal, or by internal (spinorbit coupling) and external magnetic fields. This is the key idea behind spincatalysis [17].
Activation barriers in chemical reactions are determined by the exchange repulsion between molecules in the singlet ground states. The barriers are often getting much lower when, at least, two spins are unpaired, thus when the singlettriplet transition occurs. Chemical reactivity is often coded by the triplet excited state of the molecule, in which two spins are unpaired (because exchange interaction destabilizes chemical bond in this case). Enzymatic reactions in live matter are so efficient because they often involve strong spin uncoupling induced by transition metals. This is especially important for O_{2} (dioxygen) production by photosynthesis of green plants and for dioxygen consumption by respiration of mammals.
Molecular oxygen is a vital elixir beneath the sun. Lavoisier had established that dioxygen is essential for aerobic life and is the oxidant for combustion of organic fuels. But the main puzzle of molecular oxygen is still unclear in modern biochemistry: the O_{2} molecule has a triplet ground state and how it can react with stable organic substances at 36.7 C to produce water and CO_{2} if the processes are spinforbidden? These transformations are equivalent to combustion in the net energetic and material balance. Combustion is a radical chain process. In order to burn a fuel one needs to produce a spark (to create first radical). The radical can interact with triplet O_{2} and create new radical (the brunch chain reaction). In mammals the organic food is not burned by radical chain process, since the temperature is lower than in the fire. Though the oxidation of food produces enough energy for life, the reactions are spinforbidden and can be activated and controlled by oxidase enzymes. This should involve particular spin catalysis: the strictly controlled TS transition in the enzyme active site with low activation energy, which does not produce any radicals, but only shortlived biradical intermediate. The TS transition means the subsequent spin flip in the biradical.
We present DFT calculations of the electronic structure, zerofield splitting (ZFS) and the phosphorescence spectra of biopolymers that contain chromophores being excited to the triplet state (porphyrin systems, chlorophylls and bacteriochlorophylls, aromatic amino acids, polypeptides and proteins, riboflavin, FAD, FADH_{2}, nicotinamide, NAD^{+}, NADH and active centers of glucose oxidase, copper amine oxidase, hemoglobin, horsereddish peroxidase and cytochrome P450). This is used for better understanding of the role of spectra in structural analysis of biopolymers and also for predictions of spin catalysis models in electron transfer and oxygen activation processes in these biosystems. The spin transitions are important for enzymatic reactions with and without paramagnetic transition metal involvement. Both types of spin catalysis are studied by DFT calculations of reaction models.
Our experience in fine structure calculations and spinselective photoprocesses in ZFS triplet states helps us to consider the influence of external magnetic field on the TS transitions in dark enzymatic reactions. Analysis of possible magnetic field effects on bioprocesses, including birds navigation in the Earth field, is also presented.
1. B.F. Minaev. Electronic mechanisms of molecular oxygen activation. Rus. Chem. Rev., 76 (2007) 9981023.
2. B.F. Minaev, V.A. Minaeva. Spindependent binding of dioxygen to heme. Ukrainica Bioorganica Acta,2 (2008) 5664.
3. B.F. Minaev. Solvent induced emission of singlet oxygen. J. Mol. Struct. (Theochem), 183 (1989) 207214.
4. B.F. Minaev. Intensities of spinforbidden transitions in molecular oxygen and selective heavyatom effects. Int. J. Quant. Chem., 17 (1980) 367374.
5. R. Prabhakar, P. Siegbahn, B.F. Minaev, H. Agren. Activation of dioxygen by glucose oxidase. J. Phys. Chem., B, 106 (2002) 37423750.
6. B.F. Minaev. Spin effects in reductive activation of O_{2} by oxidases. RIKEN Rev., 44 (2002) 147149.
7. B.F. Minaev, H. Agren. Spin catalysis phenomena. Int. J. Quant. Chem., 57 (1996) 510525. 

Intermonomer Interaction Effect on the Electromagnetically Induced Transparency on Molecular Aggregate Model 
Takuya Minami and Masayoshi Nakano
Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 5608531, Japan 
The intermonomer interaction effect on the electromagnetically induced transparency (EIT) for a dipolecoupled dimer model is investigated. The absorption properties are evaluated based on the imaginary part of the dynamic polarizability α using the quantum master equation approach [1]. In order to investigate the intermonomer interaction effect on the EIT, several orientations and intermonomer distances are examined. We have found that the EIT can be observed even in the presence of neardegenerete excitation states induced by the intermonomer interaction through an adjustment of the incident field frequency.
[1] M. Nakano et al., J. Phys. Chem. A 105, 22, 5473 (2001); T. Minami et al., J. Phys. Chem. C 114, 13, 60676076 (2010).


Variational path integral molecular dynamics method applied to molecular systems 
Shinichi Miura
School of Mathematics and Physics, Kanazawa University, Kakuma, Kanazawa 9201192, Japan 
Variational path integral is a method to numerically generate the exact ground state of manybody systems [1]. Recently, the author has developed a molecular dynamics algorithm for the variational path integral calculation [25], which is called the variational path integral molecular dynamics (VPIMD) method. In my talk, some applications of VPIMD to molecular systems will be presented.
References
[1] D. Ceperley, Rev. Mod. Phys. 64, 279 (1995).
[2] S. Miura, Chem. Phys. Lett. 482, 165 (2009).
[3] S. Miura, Comp. Phys. Commu. 182, 274 (2011).
[4] S. Miura, Mol. Simu. (in press).
[5] S. Miura, the ACS Symposium Series “Advances in Quantum Monte Carlo” (in press).


The potentials of the atoms around Mg^{2+} in the Hras GTP complex and in the Hras GDP complex 
Takeshi Miyakawa,^{1} Ryota Morikawa^{1}, Masako Takasu^{1}, Kimikazu Sugimori^{2}, Kazutomo Kawaguchi^{3}, Hiroaki Saito^{3} and Hidemi Nagao^{3}
^{1}School of Life Sciences, Tokyo University of Pharmacy and Life Sciences, Japan
^{2}Department of Physical Therapy, Kinjo University, Japan
^{3}Institute of Science and Engineering, Kanazawa University, Japan

In the Hras GTP complex and the Hras GDP complex, the coordination bonds between Mg^{2+} and oxygen atoms are very important. We derived the potentials of atoms around Mg^{2+} in Hras GTP complex and in the Hras GDP complex by quantum chemical calculations in order to modify the AMBER fields ff03.
Because it is not clear if SER17 and THR35 have OH group around Mg^{2+}, we consider two candidate subsystems. In one system, SER17 and THR35 have OH group, although in the other system, SER17 and THR35 have O instead of OH group. The details will be shown at the presentation.


Recent Developments in the Electron Nuclear Dynamics Theory:
From CoherentStates and DensityFunctionalTheory Implementations to Applications in Cancer Proton Therapy

Jorge A. Morales
Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX 79409 
Recent developments and applications of the electron nuclear dynamics (END) theory [1] will be presented [24]. END is a timedependent, variational, nonadiabatic method for chemical dynamics that evaluates potential energy and interatomic forces “on the fly”, without employing predetermined potential energy surfaces. The simplestlevel END (SLEND) [1] adopts a nuclear classicalmechanics description (as the zerowidth limit of frozen Gaussian wave packets) and an electronic singledeterminantal wavefunction. In the SLEND framework, three new developments will be presented:
1. The use of various types of coherentstates (CS) sets [4] to describe all types of particles (nuclei and electrons) and of degrees of freedom (translational, rotational [5], vibrational [6], and electronic). The CS sets conveniently represent the SLEND trial wavefunction and can mediate between classical and quantum descriptions. For instance, the rotational [5] and canonical [6] CS sets permit reconstructing rovibrational quantum properties from the SLEND nuclear classical dynamics. Conversely, a new CS set [2] participates in a valencebond approach to a classicalelectrostatics/chargeequilibration model based on the Sanderson principle of electronegativity equalization.
2. A new timedependent KohnSham densityfunctionaltheory (KSDFT) method in the SLEND framework: END/KSDFT [3], which incorporates electron correlation effects absent in SLEND.
3. A new implementation of effective core potentials into SLEND and END/KSDT to treat large systems.
The new developments are implemented in our code: PACE (Python Accelerated Coherentstates Electronnuclear dynamics) that utilizes several computerscience technologies [code parallelization, compute unified devise architecture (CUDA) devices, etc.]. The new developments are applied to the following chemical systems:
1. Highenergy collisions of protons with water clusters (water radiolysis) and with DNA components (direct DNA damage): these processes are highly relevant to proton cancer therapy.
2. Various protonmolecule reactions [7,8] with an emphasis on accurately predicting rovibrational, energytransfer, and electrontransfer properties.
3. Various chemical reactions involving large reactants, such as DielsAlder and SN2 reactions inter alia.
Results of the above simulations compare well with available experimental results.
References:
[1] E. Deumens, A. Diz, R. Longo, Y. Öhrn, Rev. Mod. Phys. 66 (1994) 917.
[2] J. A. Morales, J. Phys. Chem. A 113 (2009) 6004.
[3] S. A. Perera, P. M. McLaurin, T. V. Grimes, J. A. Morales, Chem. Phys. Lett. 496 (2010) 188.
[4] J. A. Morales, Mol. Phys. 108, 3199 (2010)
[5] J. A. Morales, E. Deumens, Y. Öhrn, J. Math. Phys. 40 (1999) 766.
[6] J. A. Morales, A. Diz, E. Deumens, Y. Öhrn, J. Chem. Phys. 133 (1995) 9968.
[7] B. Maiti, R. Sadeghi, A. Austin, J. A. Morales, Chem. Phys. 340 (2007) 105.
[8] B. Maiti, P. M. McLaurin, R. Sadeghi, S. A. Perera, J. A. Morales, Int. J. Quant. Chem. 109 (2009) 3026. 

Nucleation, Growth and Healing Processes of SingleWalled Carbon Nanotubes from Metal Clusters and SiO_{2} and SiC Surfaces: Density Functional TightBinding Molecular Dynamics Simulation 
Stephan Irle,^{1} Alister J. Page,^{2} Biswajit Saha,^{2} Ying Wang,^{1} K. R. S. Chandrakumar,^{2} Yoshio Nishimoto,^{1} HuJun Qian,^{1} and Keiji Morokuma^{2,3}
^{1} Institute for Advanced Research and Department of Chemistry, Nagoya University, Nagoya 4648602, Japan
^{2} Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 6068103, Japan
^{3} Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, GA 30322, U.S.A

We review our quantum chemical molecular dynamics (QM/MD)based studies of carbon nanostructure formation under nonequilibrium conditions that were conducted over the past ten years. Fullerene, carbon nanotube, and graphene formation were simulated on the nanosecond time scale, considering experimental conditions as closely as possible. An approximate density functional method was employed to compute energies and gradients onthefly in direct MD simulations, while the simulated systems were continually pushed away from equilibrium via carbon concentration or temperature gradients. We find that carbon nanostructure formation from feedstock particles involves a phase transition of sp to sp^{2} carbon phases, which begins with the formation of Yjunctions, followed by a nucleus consisting of pentagons, hexagons, and heptagons. The dominance of hexagons in the synthesized products is explained via annealing processes that occur during the cooling of the grown carbon structure, accelerated by transition metal catalysts when present. The dimensional structures of the final synthesis products (0D spheres – fullerenes, 1D tubes – nanotubes, 2D sheets – graphenes) are induced by the shapes of the substrates/catalysts, and their interaction strength with carbon. Our work prompts a paradigm shift away from traditional anthropomorphic formation mechanisms solely based on thermodynamic stability. Instead, we conclude that nascent carbon nanostructures at high temperatures are dissipative structures described by nonequilibrium dynamics in the manner proposed by Prigogine, Whitesides, and others. As such, the fledgling carbon nanostructures consume energy while increasing the entropy of the environment, and only gradually anneal to achieve their familiar, final structure, maximizing hexagon formation wherever possible. 

Effect of Confinement on the Resonance States of Atomic Systems 
J.K.Saha^{1}, T.K.Mukherjee^{1}, P. K. Mukherjee^{2,3} and B. Fricke^{4}
^{1}Narula Institute of Technology, Agarpara, Kolkata 700109, India
^{2}Department of Physics, Ramakrishna Mission Vivekananda University, Belur Math, Howrah, West Bengal 711202, India
and
^{3}Department of Mathematics, Visva Bharati University, Santiniketan, West Bengal 731 235, India
^{4}Institut fur Physik, Universitat Kassel, 34109 Kassel, Germany 
Effect of confinement on the resonance states of atomic systems, particularly for the two electron systems of different symmetries has been analysed using different theoretical methods. The type of confinement generated here is due to plasma background of different coupling strengths which lie in the domain of weak and strong coupling cases. The excited states studied here lie above the one electron continuum of the atomic systems and are doubly excited. These states lie under the energy levels corresponding to principal quantum number n>1 of the corresponding parent ion and are, in general, autoionising. For the weakly coupled plasma the Debye screening model and for the strongly coupled plasma Ion Sphere (IS) model have been used for such studies. The effect of such a confinement is to alter the potential under which the electons in the atomic system move. Schrodinger equation appropriate in such cases have been solved to obtain the ground and the doubly excited states. The plasma coupling strengths used here are such that a wide variety of plasma conditions envisaged by different temperature and number density of the plasma observed in laboratory and astrophysical context can be simulated. A number of isoelectronic ions of helium e.g. C^{4+}, Al^{11+}, Si^{12+}, P^{13+}, S^{14+}, Cl^{15+} which are of astrophysical importance have been chosen for detailed investigations using the Debye and the IS model of the plasma for the doubly excited energy levels 1s^{2}: ^{1}S^{e}> 2s^{2}:^{1}S^{e}; 2p^{2}:^{1}D^{e}, 2s2p:^{1}P^{o}, 2s3d:^{1}D^{e} and 2p3d:^{1}F^{o}. Appropriate spatial boundary conditions have been applied on the wavefunctions whenever necessary. Highly correlated calculations using Hylleraas basis sets have also been performed on He, Li^{+} and Be^{2+} on the doubly excited 2pnp:^{1,3}P^{e} and 2pnd:^{1,3}D^{e} states with n going up to 8 using Debye model of the plasma. Such data have been used for the study of transition wavelengths in appropriate cases. The general behavioural pattern of the doubly excited states under such plasma conditions has been analysed in detail. 

Electron momentum distribution and atomic collisions 
Takeshi Mukoyama
Institute of Nuclear Research of the Hungarian Academy of Sciences (ATOMKI), Debrecen, H4001 Hungary 
In quantum chemistry, the state of a physical system is usually described by a wave function in the position space. However, it is also well known that a wave function in the momentum space can provide complementary information for electronic structure of atoms or molecules. The momentumspace wave function is especially useful to analyze the experimental results of scattering problems, such as Compton profiles and ( e, 2 e) measurements. In the present work, we focus on the innershell ionization processes of atoms by chargedparticle impact and study how the electron momentum distribution affects on the innershell ionization cross sections.
The momentum wave functions in various atomic models are calculated for arbitrary atomic orbitals. The nonrelativistic hydrogenic, the HartreeFock, the relativistic hydrogenic and the DiracFock models are considered. The momentum wave functions are obtained as a Fourier transform of the wave functions in the position space. The HartreeFock and the DiracFock wave functions in atoms are given in terms of Slatertype orbitals (STO's) and all the wave functions in the momentum space can be expressed analytically in terms of hypergeometric functions.
The momentum wave functions thus obtained are used to calculate innershell ionization cross sections by chargedparticle impact in the binaryencounter approximation (BEA). The wavefunction effect and the electronic relativistic effect on the innershell ionization processes are discussed.


AB INITIO QM/MMMDFREE ENERGY GRADIENT (FEG) METHOD: FREE ENERGY LANDSCAPE OF GLYCINE ISOMERIZATION 
Masataka Nagaoka^{1,2,†}
^{1}Graduate School of Information Science, Nagoya University, Furocho, Chikusaku, Nagoya 4648601, JAPAN
^{2}Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency (JST), Honmachi, Kawaguchi 3320012, JAPAN
^{†}Email: mnagaoka@is.nagoyau.ac.jp; 
For the purpose to explore accurately the reaction paths for chemical reactions in solution or enzyme, we have proposed the free energy gradient (FEG) method [1] combined with ab initio QM/MMMD calculation [2], i.e., the ab initio QM/MMFEG method [3]. For two application, the method has been applied to the isomerization reaction of glycine in aqueous solution, i.e., the intramolecular proton transfer reaction from zwitterion (ZWcis) to the neutral form (NFcis) and other molecular structural changes among several NFs. Including the solvent effect explicitly by the ab initio QM/MMFEG method, those stablestate structures were found different from those obtained in gas phase or by an implicit dielectric continuum model at the same ab initio QM level. Additionally, by the vibrational frequency analysis with the “free energy (FE)” hessian in solution, the calculated vibrational frequencies were in good agreement with the experimental ones in the range from low to middle frequencies of ZW. Furthermore, the FE of activation from ZWcis to NFcis was found in very good agreement with not only the estimation by the CarParrinello MD method but also the previous experimental one. It is concluded that the ab initio QM/MMFEG method is promising and should provide a better description of chemical reactions in solution in comparison with a number of conventional approaches by using the mean field approximations [3]. For an application to enzymatic reactions, some recent results are also introduced.
[1] (a) N.OkuyamaYoshida, M.Nagaoka, T.Yamabe, Int. J. Quantum Chem., Vol.70, 95 (1998); (b) N.OkuyamaYoshida, K.Kataoka, M.Nagaoka, T.Yamabe, J. Chem. Phys., Vol.113, 3519 (2000); (c) M.Nagaoka, Y.Nagae, Y.Koyano, Y.Oishi, J. Phys. Chem. A, Vol.110, 4555 (2006).
[2] T.Okamoto, K.Yamada, T.Asada, Y.Koyano, N.Koga, M.Nagaoka, J. Comput. Chem, Vol.32, 932 (2011).
[3] (a) N.Takenaka, Y.Kitamura, Y.Koyano, T.Asada, M.Nagaoka, Theor. Chem. Acc., (2011) in press; (b) Y.Kitamura, N.Takenaka, Y.Koyano, M.Nagaoka, Chem. Phys. Lett., submitted. 

Functional derivative of the kinetic energy functional 
A. Nagy
Department of Theoretical Physics, University of Debrecen,
H4010 Debrecen 
Ensemble noninteracting kinetic energy functional is constructed. The differential virial theorem is derived for the ensemble. A firstorder differential equation for the functional derivative of the ensemble noninteracting kinetic energy functional is presented. A special case of the solution of this equation provides the original noninteracting kinetic energy of the density functional theory. 

Relativistic Quantum Theory for Large Systems 
Hiromi Nakai^{1} ^{2} ^{3}
^{1}Department of Chemistry and Biochemistry, Waseda University, Tokyo, Japan
^{2}Research Institute for Science and Engineering, Waseda University, Tokyo, Japan
^{3}CREST, Japan Science and Technology Agency, Tokyo, Japan 
A number of relativistic quantumchemical methods are available to treat compounds containing heavy elements. The fourcomponent relativistic theory using Dirac–Coulomb or Dirac–Coulomb–Breit Hamiltonian [1] is sufficiently accurate for describing various chemical phenomena and is therefore a good reference for examining approximate twocomponent schemes. The infiniteorder Douglas–Kroll (IODK) method [25] gives an exact description of the large component for the oneelectron Dirac Hamiltonian. The IODK/IODK method [6], which transforms twoelectron Coulomb operator by using the oneelectron IODK unitary transformation, can reproduce the total energies for the fourcomponent Dirac–Coulomb Hamiltonian even including superheavy elements. However, the computational costs for the IODK/IODK method are extremely expensive from a practical point of view.
The purpose of the present study is to propose a practical scheme for twocomponent relativistic quantumchemical calculations based on the accurate IODK/IODK method, in which the unitary transformation in a whole system is a bottle neck. We assume the locality of relativistic effect and define the local unitary transformation (LUT) [7]. The numerical tests clarify that the LUT scheme enables to reduce the computational scaling without any loss of accuracy.
In the presentation, I will explain the background of the present study, and show the formulation of the LUT scheme and the numerical results. I will also discuss the further direction of the practical relativistic quantum theory for large systems.
[1] I. P. Grant, in: S. Wilson (Ed.), Methods in Computational Chemistry, Vol. 2, Plenum Press, New York, p. 1 (1987).
[2] M. Douglas and N. M. Kroll, Ann. Phys. (Leipzig) 82, 89 (1974).
[3] B. A. Hess, Phys. Rev. A 32, 756 (1985).
[4] M. Barysz, A. J. Sadlej, and J. G. Snijders, Int. J. Quant. Chem. 65, 225 (1997).
[5] M. Barysz and A. J. Sadlej, J. Chem. Phys. 116, 2696 (2002).
[6] J. Seino and M. Hada, Chem. Phys. Lett. 461, 327 (2008).
[7] J. Seino and H. Nakai, in preparation.


OpenShell Molecular Systems for Nonlinear Optics 
Masayoshi Nakano,^{1} Ryohei Kishi,^{1} Hitoshi Fukui,^{1} Takuya Minami,^{1} Kyohei Yoneda,^{1} Shabbir Muhammad,^{1} Yasuteru Shigeta,^{1} Akihiro Shimizu,^{2} Takashi Kubo,^{2} Edith Botek,^{3} Léa Rougier,^{3} Raphaël Carion,^{3} Benoît Champagne,^{3} Kenji Kamada,^{4} and Koji Ohta^{4}
^{1}Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 5608531, Japan
^{2}Department of Chemistry, Graduate School of Science, Osaka University Toyonaka, Osaka 5600043, Japan
^{3}Laboratoire de Chimie Théorique (LCT), Facultés Universitaires NotreDame de la Paix (FUNDP) Rue de Bruxelles, 61, B5000 Namur, Belgium
^{4}Research Institute for Ubiquitous Energy Devices, National Institute of Advanced Industrial Science and Technology (AIST), Ikeda, Osaka 5638577, Japan

Over two decades, the quest for efficient nonlinear optical (NLO) materials composed of molecular systems including organic πconjugate molecules has been carried out both experimentally and theoretically. Most of the studies have been focused on the closedshell systems, while there have been few studies on the openshell systems. In the past years, we have proposed and analyzed a novel class of NLO systems, i.e., openshell singlet systems, and have theoretically elucidated that these systems exhibit strong openshell character and spin state dependences of the second hyperpolarizabilities (γ), and tend to show larger γ values in the intermediate openshell character region than conventional closedshell systems [1]. These studies are apparently worthy not only for deducing guidelines of molecular design of novel NLO systems but also for revealing fundamental relationships between the ground/excited states properties, and particularly the optical/magnetic interaction properties based on the diradical characters of chemical bonds, which are governed by electron correlation [2]. In this presentation, we briefly introduce our theoretical models involving a key factor “diradical character” and several results of the new paradigm of NLO systems based on the openshell molecular systems, including polyaromatic hydrocarbons and graphenes [3].
References
[1] (a) M. Nakano et al. Phys. Rev. Lett. 99, 033001 (2007). (b) M. Nakano et al. J. Chem. Phys. 133, 154302 (2010). (c) K. Kamada et al. J. Phys. Chem. Lett. 1, 937 (2010). (c) M. Nakano et al. J. Phys. Chem. Lett. 2, 1094 (2011).
[2] (a) K. Yamaguchi, in SelfConsistent Field : Theory and Applications, ed. R. Carbo and M. Klobukowski, Elsevier, Amsterdam, 1990, p. 727. (b) C. Lambert, Angew. Chem. Int. Ed. 50, 1756 (2011).
[3] (a) M. Nakano et al. Chem. Phys. Lett. 418, 142 (2006). (b) K. Kamada et al., Angew. Chem., Int. Ed. 46, 3544 (2007). (c) M. Nakano et al. Chem. Phys. Lett. 467, 120 (2008). (d) H. Nagai et al., Chem. Phys. Lett. 489, 212 (2010). (e) K. Yoneda et al., ChemPhysChem, 12, 1697 (2011). (f) S. Motomura et al., Phys. Chem. Chem. Phys. DOI:10.1039/c1cp20773c.


Solving the Schrödinger and DiracCoulomb equations with and without magnetic fields 
Hiroyuki Nakashima and Hiroshi Nakatsuji
Quantum Chemistry Research Institute (QCRI) and JSTCREST, Kyoto, Japan 
The free complement (FC) method is a new established method with a different concept from ordinary molecular orbital theory to solve the Schrödinger equation of atoms and molecules very accurately [1]. We have extensively studied and developed the FC method toward getting extreme high accurate wave functions for general atoms and molecules [2]. On the other hand, due to its generality of the Hamiltonian generation, the FC method is applicable to solving the relativistic DiracCoulomb equations [3] and the system in extremely strong magnetic fields [4] etc. It is rather important, for instance, astronomical physics and interstellar chemistry for the direct comparison with astronomical observations.
For correctly solving the DiracCoulomb equation, we have considered several theoretical requirements against the variational collapse problem and such as a treatment of resonance state. In the FC method, the Hamiltonian can provide a correct relationship of the multidimensional DiracCoulomb wave function (FC balance). The inverse Hamiltonian method and Hsquare quantity also with the complex scaling method [5] make numerically stable calculation possible even for the problematic DiracCoulomb equation.
We applied our methods to the systems in extremely strong magnetic fields with both nonrelativistic and relativistic levels. The Universe’s strongest magnetic field was observed on Magnetar object and the quantum mechanical calculations in magnetic fields become realistically important. In such very strong magnetic fields, we have to rely on observations in space and highly reliable theoretical studies because it is impossible to perform any experiment on the earth. We could obtain very accurate wave functions even with a strong competition between spin magnetic interaction and ordinary Coulomb force. We hope our way becomes an accurate theoretical methodology for studying unknown interesting phenomena under strong magnetic fields.
References
[1] H. Nakatsuji, J. Chem. Phys. 113, 2949 (2000). H. Nakatsuji and E. R. Davidson, J. Chem. Phys. 115, 2000 (2001). H. Nakatsuji, Phys. Rev. A 65, 052122 (2002). H. Nakatsuji, Phys. Rev. Lett. 93, 030403 (2004). H. Nakatsuji, Phys. Rev. A 72, 062110 (2005).
[2] H. Nakatsuji, H. Nakashima, Y. Kurokawa, and A. Ishikawa, Phys. Rev. Lett. 99, 240402 (2007).
[3] H. Nakatsuji and H. Nakashima, Phys. Rev. Lett. 95, 050407 (2005).
[4] H. Nakashima and H. Nakatsuji, Astrophys. J. 725, 528 (2010).
[5] G. Pestka, M. Bylicki, and J. Karwowski, J. Phys. B 39, 2979 (2006). 

Giant SACCI Method : Aperiodic System 
H. Nakatsuji and T. Miyahara
Quantum Chemistry Research Institute and JST CREST 
The SAC/SACCI method is a useful established coupledcluster type method for studying ground, excited, ionized and electron attached states of molecules [13]. It is widely distributed through Gaussian09 [4]. Giant SACCI method [5] is designed to calculate giantsize molecular systems with the same accuracy as the ordinary SACCI method of small molecules. We want to realize seamless applicability of the SACCI method from small to large and even to giantsize molecular systems.
Previously, our applications of the giant SACCI method were mainly to regular periodic systems. We here apply this method to aperiodic systems. We first apply it to an oligomer of glycine as a model of protein. The n→π* excitation energy of each C=O of glycine is different depending on its position and environment in the oligomer. Glycine does not give circular dichroism but glycine oligomer gives and the rotatory strength is dependent on the position of the monomer in the oligomer. These facts suggest that a combination of the usage of SACCI and very fine experiment may help to lead to a deeper understanding of the structure of proteins.
References
[1] Nakatsuji, H. Chem. Phys. Lett.1978, 59, 362.; 1979, 67,329,334; Bull. Chem. Soc. Jap. 2005, 78, 1705.
[2] SACCI homepage. http://www.qcri.or.jp/sacci/ (6/6/2005)
[3] Ehara, M.; Hasegawa, J.; Nakatsuji, H. Theory and applications of Computational Chemistry, The First 40 Years, Elsevior Oxford, 2005; p1099.
[4] Frisch, M. J.; et at. GAUSSIAN 09, Gaussian, Inc. Wallingford CT, 2009.
[5] H. Nakatsuji, T. Miyahara, R. Fukuda, J. Chem. Phys. 2007, 126, 084104


Controlling atomic and molecular motion with magnetic fields 
Ed Narevicius
Department of Chemical Physics,
Weizmann Institute of Science 
We will present an overview on existing methods that are able to control the center of mass motion of paramagnetic particles. We will focus on the advantage of the latest supersonic beam deceleration method, a moving magnetic trap decelerator, presenting both experimental and numerical analysis results. We will discuss possible applications and future directions.


Validation of quantum chemical methods for geometrical optimizations of sulfonamide derivatives 
Akifumi Oda,^{1,2} Yu Takano^{2} and Ohgi Takahashi^{1}
^{1}Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, Japan
^{2}Institute for Protein Research, Osaka University, Japan 
Sulfonamide is one of the most important chemical groups in drug design because sulfonamide derivatives are stable in living cells and watersoluble. In this study, we assessed the validity of quantum chemical methods and basis sets for the geometrical parameters of various sulfonamides compared to crystallographic data. Introducing ftype polarization functions into basis sets improved the geometry optimizations using HartreeFock, MP2, and B3LYP, indicating that ftype polarization functions play an important role in the description of chemical bonds in sulfonamide derivatives. 

Atomic Structure and Magnetic Anisotropy in the Small IronPlatinum Clusters: from a FirstPrinciples Study 
Tatsuki Oda^{1}, Shinya Haraguchi^{2}, and Masahito Tsujikawa^{2}
^{1}Institute of Science and Engineering, Kanazawa University, Kanazawa 9201192, Japan
^{2}Graduate School of Natural Science and Technology, Kanazawa University, Kanazawa 9201192, Japan

We have studied magnetic anisotropy in FePt, FePt2, and Fe2Pt clusters, employing a fully relativistic pseudo potential and plane wave method with the local spin density approximation. We found the stable clusters, linear and triangular ones, for both trimers. We estimated magnetic anisotropy energy from the difference of total energies, indicating that the dimer has the magnetization easy axis along the molecular axis and the linear trimers has the magnetization easy plane perpendicular to the molecular axis. We also estimated spin and orbital magnetic moments on each atom for some typical magnetization directions. 

Efficient Performance of the GRRM Method as an Explorer of Novel Reaction Channels and Chemical Structures. 
Koichi OHNO^{1} and Yuto Osada^{2}
^{1}Toyota Physical & Chemical Research Institute, Japan
^{2}Department of Chemistry, Graduate School of Sciencre, Tohoku University, Japan 
It has been believed to be impossible to search all of equilibrium structures (EQ) and transition structures (TS) by automated procedures based on quantum chemical calculations, if the number of atoms exceeds four atoms [1]. However, the global reaction route mapping (GRRM) method based on the anharmonic downward distortion (ADD) following reaction pathways made it possible to explore the entire reaction channels as well as the whole EQ and TS [2]. Although it has been claimed that a stochastic approach with repeated uses of geometrical optimization enable us mindlessly to find all chemical structures for a given chemical formula such as BCNOS [3], much more structures have been discovered by the GRRM method [4].
In this work we will demonstrate how the GRRM method [2] efficiently discovers EQs and TSs, when some parameters are varied to reduce computational demands. For limited ADD following only tracing large ADD (lADDf), ratios of the computation time, the explored number of EQ and that of TS with respect to the full ADD following (fADDf) were systematically studied. When lADDf treatments are combined with stochastic generation of starting structures, more than 80 % of EQ and 50 % of TS could be efficiently explored in one tenth of computation time with respect to that for the fADDf. This tendency of lADDf indicates promising performance of the GRRM method in its application to larger systems for finding unknown reaction pathways and new isomers.
[1] F. Jensen, Introduction to Computational Chemistry, First Ed., Wiley (1999).
[2] K. Ohno, S. Maeda, Chem. Phys. Lett. 384, 277 (2004); S. Maeda, K. Ohno, J. Phys. Chem. A 109, 5742 (2005); K. Ohno, S. Maeda, J. Phys. Chem. A 110, 8933 (2006).
[3] P. P. Bera, K. W. Sattelmeyer, M. Saunders, H. F. Schaefer III, P. v. R. Schleyer, J. Phys. Chem. A, 110, 4287 (2006).
[4] K. Ohno and Y. Osada, to be published. 

Theoretical investigation of the heterojunction effect in polymer stabilized precious metal clsuters 
Mitsutaka Okumura,^{1,2} Yasutaka Kitagawa,^{1} Takashi Kawakamai,^{1}and Shushuke Yamanaka^{1}
^{1}Department of Chemistry, Graduate School of Science, Osaka University, Japan
^{2}Core Research for Evaluational Science and Technology, Japan 
In recent years, gold is attracting industrial and scientific interests for its catalytic activity in such reactions as propylene partial oxidation, odor decomposition H2O2 direct production and CO oxidation at low temperatures, especially when Au is deposited as nanoparticles on selected metal oxides. Highly dispersed gold catalysts exhibit unique catalytic features in lowtemperature CO oxidation. In this reaction, the use of oxides of several 3d transition metals and the hydroxides of alkaline earth metals as supports leads to high activities even at a temperature as low as 203 K.
Lately, Tsukuda has found that the Au nanoclusters stabilized by poly(NVinyl2pyrrolidone) [PVP; (C_{6}H_{9}ON)_{n}] , abbreviated as Au:PVP, can oxidize phydroxybenzyl alcohol selectively into the corresponding aldehyde in water without degradation.
This observation indicates that Au cluster can exhibit high catalytic activity without any metal oxide supports. Therefore, the interaction (heterojunction) between Au cluster and PVP seems to be an important factor to oxidize benzylic alcohols to the corresponding aldehyde over the Au:PVP catalyst.
These results suggest that the heterojunctions, such as metal clustersupport junctions in heterogeneous catalysts, metalligands junctions in metal complex, active sites in enzymes, metal clusterstabilizer junction in the polymer stabilized clusters and etc., are the key factors to promote and/or modify the catalytic reaction over several types of catalysts. Therefore, we have carried out hybrid density functional theory (DFT) calculations on the heterojunction effect between Au clusters and PVP. The present theoretical study has been undertaken to explain the heterojunction effect between PVP molecules and Au clusters as a first step for understanding the heterojunction effect of the catalytic reactions over the polymer stabilized Au nanoclusters.


Origin of the variety of the Cu_{2}S_{2} core structure of the Cu_{A} sites: a density functional theory study 
Orio Okuyama^{1}, Yasuteru Shigeta^{1,2}, Haruki Nakamura^{1}, and Yu Takano^{1}
^{1}Institute for Protein Research, Osaka University, Japan
^{2}Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Japan 
The Cu_{A} site, a proximate electrontransfer intermediate from an electron source, is contained both in cytochrome c oxidase (C cO), the terminal electron acceptor in aerobic respiration, and in nitrous oxide reductase (N_{2}OR), the terminal acceptor in anaerobic respiration. The Cu_{A} site is a binuclear copper site with two bridging cystenyl thiolate groups. Each copper ion is coordinated by a histidine side chain and a methionine side chain or a carbonyl oxygen of the backbone.
Spectroscopic studies have suggested the σ_{u}* ground state of the oxidized Cu_{A} site is due to the direct Cu–Cu interaction, facilitating a rapid electron transfer over long distances with low driving forces. We have shown that the ground state of the Cu_{2}S_{2} core is the πu state even with a shorter Cu–Cu distance in the oxidized state, and that a combination of electrostatic and orbital interactions is required to stabilized the σ_{u}* state of the Cu_{2}S_{2} core rather than the π_{u} state [1].
High resolution Xray crystal structures of the Cu_{A} sites in several proteins have so far been reported. The threedimensional structures of the Cu_{2}S_{2} core of the Cu_{A} sites show various Cu–Cu or S–S distances, 2.35–2.59 Å for the Cu–Cu distance and 3.76–4.24 Å for the S–S distance. In order to elucidate the origin of the variety of the Cu_{2}S_{2} core structure of several Cu_{A} sites, we have examined electronic structures of the Cu_{2}S_{2} core of the Cu_{A} sites, using the density functional theory (DFT) with Gaussian09 program.
We built models from 10 types of C cO (PDB ID: 1V54, 1V55, 2CUA, 2GSM, 2DYR, 2EIJ, 3ABK, 3ABM, 3AG2, 3AG3), 3 types of N_{2}OR (PDB ID: 1FWX, 2IWF, 2IWK), and an engineered CuA azurin (PDB ID: 1CC3). DFT calculations were performed using the exchangecorrelation functional, M06, because the M06 functional reproduces the energy difference of the Cu_{2}S_{2} core between the σ_{u}* and πu states at the CCSD(T) level of theory. Wachters+f basis set was used for copper ions and the other atoms were treated with 6311G++(df,pd) basis set.
[1] Y. Takano, Y. Shigeta, K. Koizumi, H. Nakamura, Int. J. Quantum Chem. in press. 

ENERGY LANDSCAPES IN BORON CHEMISTRY: BOTTOMTOP APPROACH TOWARDS DESIGN OF NOVEL MOLECULAR ARCHITECTURES 
Josep M. Oliva
Instituto de QuimicaFisica "Rocasolano" (CSIC) 
Boron chemistry does not have the parallel of carbon chemistry or organic chemistry. However, the peculiar electronic configuration of boron involves a rich variety of different interactions which emerge as a voyage between the world of organic, inorganic and metal chemistry. In particular, we report on reaction mechanisms and properties of monomeric, dimeric and other (hetero)borane clusters in their ground and excited electronic states, as a base for prediction of properties of more complex boronbased molecular higher architectural constructs.
References
[1] M.F. Hawthorne, J.I. Zink, J.M. Skelton, M.J. Bayer, C. Liu, E. Livshits, R. Baer, D. Neuhauser, Science 303 (2004) 1849
[2] J. M. Oliva, N. L. Allan, P. v. R. Schleyer, C. Vińas, F. Teixidor, J. Am. Chem. Soc. 127 (2005) 13538
[3] J.M. Oliva, D.J. Klein, P.v.R. Schleyer, L. SerranoAndres, Pure Appl. Chem. 81 (2009) 719
[4] J.M. Oliva, L. SerranoAndres, Z. Havlas, J. Michl, J. Mol. Struct: THEOCHEM 912 (2009) 13
[5] L. SerranoAndrés, D.J. Klein, P.v.R. Schleyer, J.M. Oliva, J. Chem. Theory Comput. 4 (2008) 133
[6] L. SerranoAndres, J. M. Oliva, Chem. Phys. Lett. 432 (2006) 235 

Structure and dynamics of glutathione and glutathionetransferaseT22: a molecular dynamics study 
Yuriko Omae, Hiroaki Saito, Kazutomo Kawaguchi and Hidemi Nagao
Division of Mathematical and Physical Science, Graduate School of Natural Science and Technology, Kanazawa University 
Glutathione is an antioxidant concerned with the detoxification metabolism in vivo and has a function to defecate toxic compounds from cells. Glutathione transferase has been known to reduce the reactivity of toxic compounds by catalyzing their conjugation with glutathione. The function of glutathione and glutathione transferase has been through to implicate in detoxification. Thus, the understanding of the binding character between the glutathione and glutathione transferase should be important in the realization of catalytic reaction mechanism and contribute the development of antibiotic drug. In this study, we carry out the molecular dynamics simulation of glutathione transferase T22 in the presence and absence of glutathione in water solvent to analyze the dynamical structure of binding site of the ligandprotein complexes. We calculate the binding energy of the glutathione by these simulations. The specific interactions, which contribute to the binding stability of the ligand molecule, between the glutathione and glutathione transferase T22 are shown in detail by these analyses. 

Concepts of Chemical Bonding from Electron Propagator Theory 
J. V. Ortiz
Department of Chemistry and Biochemistry
Auburn University
Auburn, Alabama 368495312
U. S. A.

Ab initio electron propagator methods are a means to accurate prediction of electron binding energies of molecules and to the interpretation of spectra on the basis of accessible, oneelectron concepts. Ionization operators in Fock space provide the connection between spectra and bonding concepts. Several accurate and computationally efficient selfenergy approximations that describe orbital relaxation and electron correlation effects are now at the disposal of computational chemists. Perturbative methods, sometimes used with improved virtual orbitals, have succeeded in providing insights into the electronic structure of nucleic acid fragments and other large, organic molecules. Renormalized methods that are capable of describing qualitatively strong electroncorrelation effects have shown the limits of oneelectron pictures of spectra for fullerenes and macrocyclic compounds. They also have enabled definitive predictions on free and solvated anions with unusually delocalized patterns of electronic structure. 

Determination of Atomic Charges in Molecules and Ions 
Valentin Oshchapovsky
Lviv State University of Vital Activity Safety
35 Kleparivska Str., Lviv, 79007, Ukraine

A new method of calculation of the lattice energy of binary ionic crystals of MX type was developed [1]. It enabled to deduce a new universal formula for the lattice energy calculation taking into account only ion radii values without introducing any additional arbitrary factors. It is pointed out that the exactness of Ulat calculation depends upon the ionnity bond degree [1].
The abovementioned allowed deducting an equation for a priori calculation of the length of interatomic distances in crystals and gaseous molecules assuming that all the bonds are of pure ionic type [2].
Furthermore, the equation for the calculation of ion radii with an arbitrary effective charge was deduced [3]. The ion radii in the binary nonpolar molecules of halogens, chalcogens etc. were calculated: e.g., R^{IV}(F^{+}) = 0.255 Å, R^{IV}(Br^{+}) = 0.918 Å, R^{IV}(At^{+}) = 1.147 Å .
On the basis of these values, during the use of the previously received equation for a priori determination of interatomic distances [2] there were calculated R_{12} values for the large group of molecules of different type: halogens, interhalogenides, chalcogens, nitrogens and their combinations. It allowed to solve a reverse side of the problem i.e., to estimate the atomic charges of the large group of binary gaseous molecules according to the value of internuclear distance: Î_{2} (O^{1.92+}O^{1.92–}), ŃÎ (C^{1.76+}C^{1.76–}), CO_{2} (C^{3.68+}O^{1.84–}), N_{2} (N^{2.69+}N^{2.69–}), NO (N^{1.87+}O^{1.87–}), NO_{2} (N^{3.83+}O^{1.915–}).
Considering the experimental R12 values there were also calculated the values of atomic charges in the ionized molecules, e.g. Î_{2}^{+} (O^{2.87+}O^{1.87–}) and Î_{2}^{–} (O^{0.97+}O^{1.97–}). The radius of He^{+} ion was calculated. The possibility of estimation of ion coordination, bond multiplicity as well as some correction of ion radii R sizes is shown.
1. Oshchapovskii V.V. Russian J. of General Chemistry, 2008, V.78, No. 4, p.532542.
2. Oshchapovskii V.V. Russian J. of Inorganic Chemistry, 2010, V.55, No. 3, p. 401409.
3. Oshchapovskii V.V. Russian J. of Inorganic Chemistry (in press).


Computational study of structure, vibrational property and electrochemical reaction on a biased metalwater interface 
Minoru OTANI
Nanosystem Research Institute, National Institute of Advanced Industrial Science and Technology 
Improvement of the catalytic activity and durability of an electrode is a key issue for realizing future highefficiency fuel cell. A computer simulation is one of the important tools for this issue. We have developed a new calculation technique [1] to simulate a metalwater interface in an electrochemical environment [23]. In this talk, we describe the detail of the method and show some recent simulation results. The simulated system is composed of water and platinum (Pt). By applying a negative and positive bias to the interface, we observe variation of the surface structure and vibrational frequency shift of the OH stretching mode of water molecules. Spontaneous electrochemical reactions are simulated within our model.
[1] M. Otani and O. Sugino, Phys. Rev. B 73, 115407 (2006).
[2] O. Sugino, et al., Surf. Sci. 601, 5237 (2007); M. Otani, et al., J. Phys. Soc. Jpn. 77, 024802 (2008); M. Otani, et al., Phys. Chem. Chem. Phys. 10, 3609 (2008).
[3] T. Ikeshoji, M. Otani, I. Hamada, and Y. Okamoto, Phys. Chem. Chem. Phys. submitted.


Electronic structure calculations on vacancymanganese center in nanodiamond systems 
Takao Otsuka,^{1} Yoshitaka Tateyama,^{2,3} Masahito Morita,^{4} Makoto Taiji^{1}
^{1}RIKEN Quantitative Biology Center (QBiC), Kobe, Hyogo, Japan
^{2}International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), Tsukuba, Ibaraki, Japan
^{3}CREST, Japan Science and Technology Agency (JST), Kawaguchi, Saitama, Japan
^{4}WPI Immunology Frontier Research Center (iFReC), Osaka University, Suita, Osaka, Japan

We present our theoretical study on vacancymanganese center in nanodiamond systems by electronic structure calculations. We investigate the stability of spin states in some vacancymanganese complexes in nanodiamond by using cluster models calculations. From the analysis of electronic structures by density functional theory (DFT) and HartreeFock with the perturbative correction calculation (with unrestricted/restricted openshell), we found that the high spin state of [VMnV] complex is most probable among different spin states and defect types. The results on the surface oxidation systems will be also reported. 

Application of Variational Principle to the Dirac Equation 
Grzegorz Pestka
Institute of Physics, Nicolaus Copernicus University, Torun, Poland 
In the variational determination of the Dirac Hamiltonian eigenstates a major problem which has to be taken into consideration is the "variational collapse". Commonly by the "variational collapse" we understand unlimited decrease of some variational eigenvalues, but in general under this abbreviated name we can understand a broader set of problems related to an improper choice of the variational space. Thus, in general, "variational collapse" also contains such effects in the calculated spectrum as a wrong order of eigenstates, convergence to wrong eigenstates, or appearance of spurious states. All these effects can appear also if the basis set approaches completeness, i.e. it would be correct if we aimed at solving a bounded from below eigenvalue problem.
In this talk a survey of problems related to the correct construction of the basis sets in unbounded from below eigenproblems involving multicomponent eigenfunctions will be presented. In particular, the importance of the exact balance between the large and small component variational spaces in the DiracPauli representation of the Dirac equation will be explained. As a consequence of the way the balance between the spaces has been formulated, the problem of the boundary conditions will be elucidated.


Recent Advances in Renormalized and ActiveSpace CoupledCluster Methods 
Piotr Piecuch,^{1} Jun Shen,^{1}, Marta Włoch,^{2}Jesse J. Lutz,^{1}, Jeffrey R. Gour,^{3} and Wei Li^{4}
^{1}Department of Chemistry, Michigan State University, East Lansing, Michigan 48824, USA
^{2}Department of Chemistry, Michigan Technological University, Houghton, Michigan 49931, USA
^{3}Department of Chemistry, Stanford University, Stanford, California 94305, USA
^{4}School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu 210093, China 
The widely used coupledcluster (CC) and equationofmotion (EOM) CC methods, such as CCSD(T) and EOMCCSD, have difficulties with capturing stronger nondynamic electron correlations characterizing chemical reaction pathways and excited states dominated by twoelectron transitions that can often be addressed by exploiting the completely renormalized (CR) and activespace CC and EOMCC approaches. This talk will discuss recent advances in the development and applications of the CR and activespace CC/EOMCC methods, including the extension of the former approaches to larger reactive molecular systems via the local correlation clusterinmolecule ansatz and its multilevel extension, and the exciting new possibility of merging the CR and activespace methodologies into a single mathematical formalism that leads to further improvements of the results for potential energy surfaces along bond breaking coordinates. The latter idea requires the generalization of the moment energy expansions that are behind the CRCC methods to nontraditional truncations of the cluster operator and related excitation manifolds. 

Koopmans' theorem in the ROHF method. General formulation 
Boris N. Plakhutin
Laboratory of Quantum Chemistry, G.K.Boreskov Institute of Catalysis, Russian Academy of Sciences
Novosibirsk 630090, Russia 
A general formulation of Koopmans’ theorem (KT) is derived in the ROHF method for molecular and atomic systems with arbitrary orbital occupancies and total electronic spin. The key point of the formulation is the new variational condition introduced in the ROHF method in addition to the familiar variational principle.
The new condition ensures the stationarity of the ionized energy (i.e., of the ionization potential or electron affinity) defined in Koopmans’ approximation with respect to a variation of orbitals within the ionized electronic shell. Taken together, the variational principle and the new condition define the special ( canonical) form of the ROHF Hamiltonian whose eigenvalues (orbital energies) satisfy KT for the whole energy spectrum.
The talk will focus on the deep relation between the variational conditions underlying the present (canonical) ROHF method and the limited configuration interaction (CI) approach. The practical applicability of the theory is verified by comparing the KT estimates [4] of the vertical ionization potentials I_{2s} and I_{2p} and electron affinities A_{2p} for the second row openshell atoms (Li to F) with the respective experimental data. This study was supported by the Russian Fund for Basic Research (grant 090300113) and the Russian Academy of Sciences (grant OXHM/5.1.9).
1. B.N. Plakhutin, E.V. Gorelik, and N.N. Breslavskaya, J. Chem. Phys. 125, 204110 (2006).
2. B.N. Plakhutin and E.R. Davidson, J. Phys. Chem. A. 113, 12386 (2009).
3. E.R. Davidson and B.N. Plakhutin, J. Chem. Phys. 132, 184110 (2010).
4. B.N. Plakhutin, submitted.


Timedomain ab initio studies of excitation dynamics in semiconductor quantum dots 
Oleg Prezhdo
University of Rochester 
Solar energy applications require understanding of dynamical response of novel materials on nanometer scale. Our stateoftheart nonadiabatic molecular dynamics techniques, implemented within timedependent density functional theory, allow us to model such response at the atomistic level and in real time. The talk will focus on single and multiple exciton generation, relaxation, annihilation and dephasing in semiconductor quantum dots.
1. O. V. Prezhdo, “Multiple excitons and electronphonon bottleneck in semiconductor quantum dots: Insights from ab initio studies”, Chem. Phys. Lett. – Frontier Article, 460, 1 (2008)
2. O. V. Prezhdo “Photoinduced dynamics in semiconductor quantumdots: insights from timedomain ab initio studies”, Acc. Chem. Res., 42, 2005 (2009)
3. A. B. Madrid, H.D. Kim, O. V. Prezhdo, “Phononinduced dephasing of excitons in silicon quantum dots: multiple exciton generation, fission and luminescence”, ACSNano, 3, 2487 (2009)
4. C. M. Isborn, O. V. Prezhdo, “Quantum dot charging quenches multiple exciton generation: firstprinciples calculations on small PbSe clusters”, J. Phys. Chem. C, 113, 12617 (2009)
5. S. V. Kilina, D. S. Kilin, O. V. Prezhdo, “Breaking the phonon bottleneck in PbSe and CdSe quantum dots: timedomain density functional theory of charge carrier relaxation”, ACSNano, 3, 93 (2009).
6. S. A. Fischer, A. B. Madrid, C. M. Isborn, O. V. Prezhdo, “Multiple exciton generation in small Si clusters: A highlevel, ab initio study”, J. Phys. Chem. Lett., 1, 232 (2010).


Fundamental Symmetries and Symmetry Violations from High Resolution Molecular Spectroscopy: Experiment and Theory 
Martin Quack
ETH Zurich, Physical Chemistry, Switzerland

High resolution molecular spectroscopy in combination with appropriate theoretical analysis provides a route to fundamental physics, which complements the standard approaches of high energy physics [1]. In the lecture we shall first address general aspects of fundamental symmetries in physics and their violations. We shall then present recent theoretical and experimental progress from the work of our group concerning parity violation in chiral molecules [2] and nuclear spin symmetry conservation and violation in molecules with several identical nuclei based on approaches formulated a number of years ago, but bringing fruit now [1, 3, 4]. If time permits, we conclude with speculations on CPT violation and on dark matter [1, 5].
[1] M. Quack, Fundamental Symmetries and Symmetry Violations from High Resolution Spectroscopy in Handbook of High Resolution Spectroscopy (Eds.: M. Quack, F. Merkt), Wiley, Chichester, New York, 2011, in press.
[2] M. Quack, J. Stohner, M. Willeke, Annu. Rev. Phys. Chem. 2008, 59, 741769.
[3] M. Quack, Mol. Phys. 1977, 34, 477504.
[4] M. Quack, Chem. Phys. Lett. 1986, 132, 147153.
[5] M. Quack, Chem. Phys. Lett. 1994, 231, 421428.


Modeling Magnetic Anisotropy of Single Molecule Magnets 
S. Ramasesha
Solid State and Structural Chemistry Unit
Indian Institute of Science
Bangalore, 560012, India 
We present a theoretical approach for solving the exchange Hamiltonian of a system with assorted isotropic spins. This approach is based on the use of a dual basis set that exploits the ease of constant MS basis in spatial symmetry adaptation and the valence bond (VB) basis for spin adaptation1,2. Using this method, the Hamiltonian of a system, for any arbitrary point group in any chosen spin space, can be fully block diagonalized. We use the eigenstates so obtained to compute the molecular magnetic anisotropy parameters, DM and EM for single molecule magnets in the desired eigenstate of the exchange Hamiltonian, treating the anisotropic interactions as a perturbation3.
References:
1.S. Sahoo, R. Rajamani, S. Ramasesha and D. Sen, Phys. Rev. B, 78, 054408 (2008).
2.S. Sahoo and S. Ramasesha, Int. J. Quantum Chem. DOI 10.1002/qua23097 (2011).
3.R. Raghunathan, S. Ramasesha and D. Sen, Phys. Rev. B, 78, 104408 (2008). 

THE CONTRIBUTION OF QUANTUM CHEMISTRY TO THE PHOTODYNAMIC THERAPY 
Nino Russo
Dipartimento di Chimica and Centro di Calcolo ad Alte Prestazioni per Elaborazioni Parallele e DistribuiteCentro d’Eccellenza MURST, Universitŕ della Calabria, I87030 Arcavacata di Rende, Italy. Email: nrusso@unical.it 
The performance of density functional based methods to characterize and design new photosensitizers active in photodynamic therapy starting from computed chemical physics electronic and geometrical properties by using the density functional theory is presented. In particular, we were concerned with a series of molecular systems able to activate the singlet O2 excited state (Type II reactions) [1]. The investigated properties include the energy gap between ground and excited states with different spin multiplicities (SingletTriplet) and the electronic excitation energies (Q band of the UVVis spectra). In addition the way to compute the spinorbit couplings that allow the possible intersystem crossing is presented and discussed [2].
Work performed with the financial support of Universitŕ della Calabria and MIUR (PRIN 2008F5A3AF_005).
References
[1] L. Petit, C. Adamo and N. Russo, J. Phys. Chem. B 109 (2005) 1221412221.; L. Petit, A. D. Quartarolo, C. Adamo, N. Russo, J. Phys. Chem. B, 110 (2006) 23982404.; A. Quartarolo, N. Russo and E. Sicilia, Chem. Eur. J. 12 (2006) 67976803.; A. D. Quartarolo, N. Russo, E. Sicilia and F. Lelj, J. Chem. Theory Comput. 3 (2007) 860869; Lanzo, I.; Russo, N.; Sicilia, E., J. Phys. Chem. B., 112 (2008) 41234130; I. Lanzo, A. D. Quartarolo, N. Russo and E. Sicilia, Photochem. Photobiol. Sci., 8 (2009) 386 – 390; A. D. Quartarolo, E. Sicilia and N. Russo, J. Chem. Theor. Comput. 5 (2009) 18491857; A. D. Quartarolo, I. Lanzo, E. Sicilia and N. Russo, Phys. Chem. Chem. Phys., 11, (2009) 4586 – 4592.
[2] S. Chiodo and N. Russo, J. Comput. Chem. 29 (2008) 912920; S. G. Chiodo, N. Russo, J. Computat. Chem. 30 (2009) 832839; S. Chiodo and N. Russo, Chem. Phys. Lett. 490 (2010) 9096; A. D. Quartarolo, S. G. Chiodo, and N. Russo, J. Chem. Theory Comput., 6 (2010) 3176–3189.


Interactions with electromagnetic fields: The frequencydependent magentizability 
Marco Anelli, Dan Jonsson and Kenneth Ruud
Centre for Theoretical and Computational Chemistry
Department of Chemistry
University of Tromsř
N9037 Tromsř
Norway 
Materials with a negative index of refraction are substances in which either one or both of the permittivity and the permeability of the medium is negative. Whereas the permittivity of the medium is well defined and related to the frequencydependent polarizability, the dispersion behaviour of the permeability is not as well defined. The relation between the macroscopic permeability and the microscopic quantity describing the interaction with the magnetic component of the electromagnetic field, the frequencydependent magnetizability, is in contrast poorly understood. Indeed, even the definition of the frequencydependent magnetizability appear unsatisfactory.
A theory for the frequencydependent magnetizability has been presented by Raab and de Lange [1], and these authors have also considered the frequencydependent permeability [2]. However, the expression derived for the frequencydependent magnetizability is based on a number of assumptions, making the theory somewhat unsatisfactory.
In this talk, we will discuss our recent analysis of the frequencydependent magnetizability, and propose a new way of deriving the frequencydependent permittivity, inverse permeability and magnetizability starting from an analysis of the currentcurrent response function.
[1] R.E.Raab and O.L.de Lange. Mol.Phys. 104, 1925 (2006).
[2] R.E.Raab and O.L.de Lange. Proc.~Royal Soc. 461, 595 (2005). 

Calculation of Energy Deposition by Swift Ions in Biomolecules: Glycine to DNA 
John R. Sabin,^{1,2} Stephan P. A. Sauer,{3 and Jens Oddershede^{1,2}
^{1}Department of Physics and Chemistry, University of Southern Denmark, Odense Denmark
^{2}Quantum Theory Project, Department of Physics, University of Florida, Gainesville, Florida, USA
^{3}Department of Chemistry, University of Copenhagen, Copenhagen, Denmark 
The effects of energy transfer from swift ion radiation to biomolecules are best described by the stopping cross section of the target molecule for the projectile ion. In turn, the mean excitation energy of the target is the determining factor in the stopping cross section. Using polarization propagator methodology, the mean excitation energies of components of several biomolecular systems, ranging from amino acids to nucleotides have been calculated, and are reported here. The calculated mean excitation energies could then be used to determine the stopping cross sections of the various biomolecular systems.


Free energy profile of water across cholesterol containing lipid bilayer 
Hiroaki Saito^{1,3} and Wataru Shinoda^{2,3}
^{1} Faculty of Mathematics and Physics, Institute of Science and Engineering, Kanazawa University, Kanazawa 9201192 Japan
^{2} Nanosystem Research Institute (NRI), Research Institute of Advanced Industrial Science and Technology (AIST), Central 2, 111 Umezono, Tsukuba 3058568, Japan
^{3} CREST, Japan Science and Technology Agency (JST), 418 Honcho, Kawaguchi, Saitama 3320012, Japan

The free energy profiles of a water molecule across two different lipid bilayers of dipalmitoyl phosphatidylcholine (DPPC) and palmitoyl sphingomyelin (PSM) in the absence and presence of cholesterol (050 mol%) have been studied by molecular dynamics simulations to elucidate the molecular mechanism of the reduction in water leakage across the membranes by the addition of cholesterol. An enhanced free energy barrier was observed in these membranes with increased cholesterol concentration, and this was explained by the reduced cavity density around the cholesterol in the hydrophobic membrane core. There was an increase of trans conformers in the hydrophobic lipid chains adjacent to the cholesterol, which determined the cavity density. At low cholesterol concentrations the PSM bilayer exhibited a higher free energy barrier than the DPPC bilayer for water permeation, while at greater than 30 mol% of cholesterol the difference became minor. This tendency for the PSM and DPPC bilayers to resemble each other at higher cholesterol concentrations is similar to commonly observed trends in several structural properties, such as order parameters, crosssectional area per molecule, and cavity density profiles in the hydrophobic regions of bilayer membranes. These results demonstrate that DPPC and PSM bilayers with high cholesterol contents possess similar physical properties, which suggests that the solubility of cholesterol in these lipid bilayers has importance for an understanding of multicomponent lipid membranes with cholesterol. 

FirstPrinciples Calculations of Defects in Graphenes and Carbon Nanotubes 
Mineo Saito, Kazuyuki Nishida, and Jianbo Lin
Division of Mathematical and Physical Sciences, Graduate School of Natural Science and Technology,Kanazawa University, Kakuma Kanazawa 9201192, Japan 
Graphene and carbon nanotubes (CNT) are candidates for nanodevice materials. Then, control of defects and impurities in graphene and CNT is necessary when these nano carbon materials are used as parts of nanodevices. In this study, we carry out firstprinciples calculations on defects and impurities in the singlelayer graphene and singlewall CNT. The spinpolalized density functional calculations are performed. In the case of adatomvacancy pair, we find that its healing barrier to the perfevt material is in the range 0.06eV0.5 eV. These results are consisten with an experimental value (0.3 eV) in the case of singlewall CNT. 

Modifications for the electron and the polarization propagator formalisms 
Masaaki Saitow^{1}, Tomonori Ida^{2}, and Yuji Mochizuki^{1}
^{1} Department of Chemistry and Research Center for Smart Molecules, Rikkyo University, 3341 Nishiikebukuro, Toshimaku, Tokyo 1718501, Japan
^{2} Department of Chemistry, Kanazawa University, Kakumamachi, Kanazawa 9201192, Japan 
We have derived some improvements for the ab initio Green's function formalisms including the electron and the polarization propagators. For the former case, which describes oneelectron detachment process, a spin adapted formalism was derived by considering spincoupling of the configuration space explicitly. And this approach gives improved description for the openshell species over the conventional method, although the working equation become rather cumbersome because of the structure of the spin functions. And for the polarization propagator theory, two distinct modifications for the second order framework are shown. The first approach is specifically effective for the Rydberg excitation, in which drastic rearrangement of the charges occur, and recognizable as a branch of denominator shift approach. The second approach improves the differential correlation in terms of the ground and excited states and gives good results for the strongly degenerated states. Both methods retain the polynomial scaling to O(N^5) .


Evaluation of multicenter integrals of Slater type orbitals and CoulombYukawa like electric field gradient potentials using their onerange addition theorems 
Nursen SECKIN GORGUN
Faculty of Science, Department of physics, Trakya university, Edirne, Turkey 
Using onerange addition theorems established in Ref.[1] for Slater type orbitals and CoulombYukawa like interaction potentials with the help of complete orthonormal sets of ψ^αexponential type orbitals (α=1,0,1,2,…) [2], the calculations are performed for multicenter electric field gradient integrals. The results of computations show good rate of convergence and numerical stability. The convergences of the series is tested by calculating multicenter electric field gradient integrals for the arbitrary values of parameters of potentials and location of orbitals.
[1] I. I. Guseinov, Bull. Chem. Soc. Jpn., 78 (2005) 611
[2] I. I. Guseinov, Int. J. Quantum Chem. ,90 (2002) 114


Cluster Embedding Method with NonOrthogonal Wave Functions: DFT KohnSham Embedding Equations and Vacant States 
Emma K. Shidlovskaya^{1,2}
^{1}Information Systems Management Institute, Riga, Latvia
^{2}Institute of Chemical Physics, University of Latvia, Riga, Latvia 
When we theoretically study processes in large or infinite electron systems we have to treat the whole quantum system as two subsystems: small fragment of the system (cluster) and the remaining part of it. Problem "cluster in the field of the rest of system" is successfully solved in the frameworks of embedded molecular cluster (EMC) model [1] with orthogonal wave functions. Unfortunately, standard realization of EMC model leads to wellpronounced boundary effects [2].
To overcome limitations of the standard EMC model, we have treated cluster embedding problem in the frameworks of oneelectron approximation with nonorthogonal wave functions. Equations for the cluster are obtained varying total energy of the system expressed in terms of nonorthogonal oneelectron wave functions. Using these cluster embedding equations we have developed modified cluster embedding scheme. We have demonstrated that application of this scheme may radically reduce boundary effects in EMC model [2].
Possibility to generalize our embedding approach on the case of DFT KohnSham oneelectron equations is studied. We demonstrate that our variation procedure is compatible with KohnSham method. Cluster embedding equations remain the same [3] if instead of Fock operator we use oneelectron KohnSham Hamiltonian.
For further applications of our cluster embedding method we should overcome limitations of oneelectron approximation. It may be done by configurations interaction (CI) or perturbation theory (PT) methods. For this purpose we need occupied and vacant cluster states of the same localization. We have established that our initial embedding equations [2] give localized in the cluster region occupied states and delocalized vacant ones [4]. To get the same localization degree for the both occupied and vacant states, modified equations are proposed [4].
Modified cluster embedding equations [4] lead to correct description of electron transitions from occupied states to vacant ones. Treatment of electron correlation effects by CI or PT and proper description of excited states both by CI or DFT become possible. As the result, our embedding scheme now may be applied for quantumchemical simulation of various phenomena.
[1] L.N.Kantorovich, J. Phys. C: Solid State Phys. 21, 5041 (1988).
[2] E.K. Shidlovskaya, Int. J. Quantum Chem. 89, 349 (2002).
[3] E.K. Shidlovskaya, in Topics in Chemistry and Material Science, Volume 2. Theoretical Aspects of Catalysis, eds. G. Vayssilov, T. Mineva, Heron Press, Sofia, 2009, pp. 1118.
[4] E.K. Shidlovskaya, Computer Modelling and New Technologies 10, No 4, 17 (2006).


Classical and Quantal Cumulant Mechanics 
Yasuteru Shigeta
Department of Material Sciences, School of Engineering Science, Osaka University 
We have proposed a quantal cumulant dynamics (QCD) method for the investigation of weak quantum effects on model and molecular systems including proton transfer reactions [14]. The essence of this method is to treat with an extended dynamics of distribution characterized as expectation values generating from the distribution. Within this scheme, not only the position and momentum but also the cumulant variables, which are functions of mixed position and momentum moment operators plays central role in its propagation. We generalized the same procedures to treat problems appearing in classical statistical mechanics. We applied these methods to investigate melting behavior of small Morse clusters.
References
[1] Y. Shigeta, H. Miyachi, K. Hirao, JCP 125, 244102 (2006).
[2] Y. Shigeta, JCP 128, 161103(2008).
[3] Y. Shigeta, T. Matsui, H. Miyachi, K. Hirao, BCSJ 81, 1230 (2008).
[4] Y. Shigeta, a book chapter of “Advances in the Theory of Atomic and Molecular Systems”, Ed. P. Piecuch, J. Maruani, G. DelgadoBarrio, S. Wilson, Springer (2009).


RealTime TDDFT Simulation for Coherent Phonon Generation 
Yasushi Shinohara^{1}, Kazuhiro Yabana^{1,2}, JunIchi Iwata^{2}, Tomohito Otobe^{3} and George F. Bertsch^{4}
^{1}Graduate School for Pure and Applied Sciences, University of Tsukuba, Japan
^{2}Center for Computational Sciences, University of Tsukuba, Japan
^{3}Advanced Photon Research Center, Japan Atomic Energy Agency, Japan
^{4}Department of Physics, University of Washington, USA 
We have been developing a firstprinciples description for quantum dynamics of electrons and ions induced by an intense and ultrashort laser pulse. In our method, electron dynamics is described by the timedependent densityfunctional theory (TDDFT) solving the timedependent KohnSham equation in realtime, while the ion motion is described by classical mechanics with the force evaluated by the Ehrenfest theorem. We consider a dynamics under a spatiallyuniform electric field which includes the polarization field as well as the applied electric field. Our scheme is capable of describing dielectric function in the linear response regime [1]. It has also been applied to optical breakdown in nonlinear regime [2].
In my presentation, we report an application of our framework for coherent phonon generation in bulk Si [3]. Coherent phonon is a macroscopic lattice vibration induced by the ultrashort laser pulse whose duration is shorter than the vibration period.
The figure below shows the calculated force acting on optical phonon coordinate at photon frequencies of 2.25, 2.5 and 2.75 eV. In our calculation, direct band gap of bulk Si is 2.4 eV. When the laser frequency is below the direct band gap (2.25 eV, red solid line), the impulsive force is only seen during the irradiation of the laser pulse (016 fs). When the laser frequency is above the direct band gap (2.75 eV, blue dotted line), the force persists even after the laser pulse ends. These features are consistent with two mechanisms of coherent phonon generation which have been proposed in phenomenological studies, the impulsive stimulated Raman scattering (ISRS) and the diplacive excitation of coherent phonon (DECP). In the ISRS, the force is generated from virtual electronhole excitations. In the DECP, the force is generated from real electronhole excitations which persist even after the laser pulse ends. We thus conclude that, in our framework based on TDDFT, both mechanisms of ISRS and DECP are included in a unified way.
We also apply the method to semimetal, Sb. Preliminary results will be presented as well.
[1] G.F. Bertsch, J.I. Iwata, A. Rubio and K. Yabana, Phys. Rev. B 62, 7998 (2000)
[2] T. Otobe, M. Yamagiwa, J.I. Iwata, K. Yabana, T. Nakatsukasa and G.F. Bertsch, Phys. Rev. B 77,165104 (2008)
[3] Y. Shinohara, K. Yabana, Y. Kawashita, J.I. Iwata, T. Otobe and G.F. Bertsch, Phys. Rev. B 82, 155110 (2010)

Figure. The force on the optical phonon coordinate for three laser frequencies: 2.25 eV (red solid); 2.5 eV (green dashed); and 2.75 eV (blue dotted).



Piezoelectricity 
Michael Springborg and Bernard Kirtman
Physical and Theoretical Chemistry, University of Saarland, Campus B2.2, 66123 Saarbrücken, Germany
Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, U.S.A. 
Piezoelectricity results from a coupling between responses to mechanical and electric perturbations. Conveniently, it can be studied theoretically by analysing the change in the dipole moment due to strain or stress. However, whereas the definition of the operator for the dipole moment for any finite system, independent of its size, is trivial, it is only within the last 1  2 decades that the expressions for the equivalent operator in the independentparticle approximation for the infinite and periodic system have been proposed. We indicate how these expressions can be derived and which approximations are involved. We demonstrate that the so called branch dependence of the dipole moment per unit for the infinite and periodic system is related to physical observables in contrast to what often is assumed. Finally, again in contrast to common assumptions, we argue that the dipole moment per unit may change branch abruptly. This is related to the finding that piezoelectric properties depend both on the terminations and on the shape of the samples of interest even for samples with size well above the thermodynamic limit. 

Theoretical study of isotopeinduced additivity of chemical shift in benzene 
Kimikazu Sugimori,^{1} Hiroyuki Kawabe^{2}, and Hideto Shimahara^{3}
^{1}Department of Physical Therapy, Faculty of Health Sciences, Kinjo University, Japan
^{2}Department of Social Work, Faculty of Social Work, Kinjo University, Japan
^{3}Center for Nano Materials and Technology, Japan Advanced Institute of Science and Technology, Japan 
The isotope effect induced by deuterium substituted species is observed in molecular properties, such as geometry, kinetics, and electronic state of the molecules through nuclearelectron interaction. Theoretical considerations and experimental alignments have been studied by ab initio molecular orbital (MO), density functional (DF) theory, and other empirical strategies. The BornOppenheimer (BO) approximation with nuclear vibrational wavefunction can treat isotope effect because nuclear mass effect account for the average distance of vibrational motion [1]. We have been reported for diatomic molecules [2].
In this study, we apply Morse anharmonic oscillator model to calculate average internuclear distance of isotopologues and isotopomers of methanlike molecules and benzene derivatives. NMR shielding constants are calculated again on the average distance by using GaugeIndependent Atomic Orbital (GIAO) method with B3LYP/ccpVTZ and CCSD/ccpVTZ. The calculated isotope shifts will be discussed with relation to additivity, charge distribution, and experimental values.
References
[1] A. C. de Dios and C. J. Jameson. Annu. Rep. NMR Spectrosc. 29 (1994) 169.
[2] K. Sugimori and H. Kawabe, Int. J. Quantum Chem. 110 (2010) 29892995. doi: 10.1002/qua.22917


ComputerModeling Study on Molecular Sorption Patterns in Porous Materials: For Strategic Design of Porous Coordination Polymers 
Manabu Sugimoto
Graduate School of Science and Technology, Kumamoto University 
Porous coordination polymers (PCPs), which are also known as metalorganic frameworks (MOFs), are threedimensionally extended coordination compounds consisting of metal ions and organic ligands. In synthesis, multidentate organic linkers are used so that the resultant PCP/MOF crystal is porous with nanosized pores of 150 nm. Recent works have been showing that PCP/MOF is one of the promising functional materials in versatile fields in Chemistry and Materials Science: for example, it is considered of as a potentially important material for hydrogengas storage in fuel cell systems.
PCPs/MOFs are synthesized through selfassembly of component ions and molecules. Therefore their framework structures directly reflect the chemical topology of the components. This suggests that rational design of molecular framework is of critical importance in materials design and synthesis. Once we would design reasonable topology of the framework to improve its functionality, we would be able to choose appropriate metal ions and organic molecules from many textbooks and/or compound catalogues.
In this work, we aim at (hopefully) establishing a design strategy of PCP/MOF through Monte Carlo simulations based on simplified hostguest systems. In our simulations, the hostguest interaction and topology of pores of model host compounds are systematically modulated. Through computer modeling, it will be shown that manybody (multisite) interaction would be of essential importance for highly condensed gas sorption. It will also be pointed out that topological singularity might contribute to unique gas separation.


Development of FirstPrinciples Maxwell+TDDFT MultiScale Simulator for
Propagation of HighIntensity Laser Pulse 
Takeru Sugiyama^{1},Yasushi Shinohara^{1},Tomohito Otobe^{2},Kazuhiro Yabana^{1,3} and George F. Bertsch^{4}
^{1}Graduate School for Pure and Applied Sciences, University of Tsukuba, Japan
^{2}Center for Computational Sciences, University of Tsukuba, Japan
^{3}Advanced Photon Research Center, Japan Atomic Energy Agency, Japan
^{4}Department of Physics, University of Washington, USA 
Interaction between light and matter is described by the Schroedinger and Maxwell equations. The Schroedinger equation describes electron dynamics while the Maxwell equation describes propagation of electromagnetic fields. For ordinary weak lightwave, one can apply the perturbation theory for the Schroedinger equation which decouples two equations with the dielectric function. However, for intensive laser pulses, one cannot separate them because of the nonlinear electron responses to the strong electric field of the laser pulse. Previously, we developed a framework in TDDFT to describe electron dynamics under spatiallyuniform timevarying electric field solving the timedependent KohnSham equation in realtime [1,2]. We now extend it to a firstprinciples simulator calculating simultaneously the coupled nonlinear dynamics of electrons and electromagnetic field. Since the lengthscale is much different between the laser wavelength (μm) and the electron dynamics (nm), we employ two different spatial grids and express the vector potential in the macroscopic grids and the KohnSham orbitals in the microscopic grids. As a preliminary demonstration, we will show our calculation for the one dimensional propagation of electromagnetic field incident on bulk Si.
[1]T. Otobe et al. Phys.Rev.B77,165104(2008)
[2]Y. Shinohara et al. Phys.Rev.B82,155110(2010)

Figure. Laser pulse irradiated on bulk Si surface. The intensity and the frequency of the laser pulse is set to I=5×10^{12}W/cm^{2} and ℏw=1.55eV (below calculated bandgap, 2.4eV), respectively. The upper panels show propagation of electromagnetic field. The lower panels show the groundstate electron density (left) and the density change of electrons from that in the ground state at the surface (middle and right).



A sideways glance at the Born and BornOppenheimer approximations 
Brian T Sutcliffe
Service de Chimie quantique et Photophysique,
Univ. Libre be Bruxelles,
1050 Bruxelles, Belgium.

The Born and BornOppenheimer papers are looked at again in the light of new approaches made possible by developments in mathematical techniques made since their original publication.
How these techniques may be applied to a diatomic system will be detailed but it will be explained why it is not possible at present to extend these techniques to a polyatomic system. It is concluded that in general the BornOppenheimer approximation cannot yet be regarded as securely founded mathematically.


Multi component molecular theory for hydrogen bonded systems and positronic compounds

Masanori Tachikawa and Yukiumi Kita
YokohamaCity University 
Recently, we have developed some firstprinciples approaches for multicomponent systems including both electrons and nuclei (or positron) quantummechanically: (I) Multicomponent molecular orbital (MC_MO) [1,2], DFT (MC_DFT) [3], quantum Monte Carlo (MC_QMC) [4], and (II) ab initio path integral molecular dynamics (PIMD) [5,6] methods.
First, we demonstrated that HCN, as the simplest nitrile molecule, can bind a positron by the most accurate QMC approach [4]. We have also found that the positron affinity (PA) value of acetonitrile with electronic 631++G(2df,2pd) and positronic [15s15p3d2f1g] basis set with the CI scheme of MC_MO method is calculated as 4.96 mhartree [2], which agrees to within 25% with the recent experimental value of 6.6 mhartree by Danielson et al. [7].
Next, we will show some theoretical aspects of path integral simulation with 2nd and 4th order Trotter expansion. Then, we will show some computational results with PIMD simulation for the H/D isotope effect on deprotonated water dimer anion H_{3}O_{2}^{} [5,6] and the mechanism of double proton transfer in porphycene molecule [8].
References
[1] T. Ishimoto, M. Tachikawa, and U. Nagashima, J. Chem. Phys., 124, 014112 (2006).
[2] M. Tachikawa, Y. Kita, and R. J. Buenker, Phys. Chem. Chem. Phys., 13, 27012705 (2011).
[3] T. Udagawa and M. Tachikawa, J. Chem. Phys., 125, 244105 (2006).
[4] Y. Kita, R. Maezono, M. Tachikawa, M. Towler, and R. J. Needs, J. Chem. Phys., 131, 134310 (2009).
[5] M. Tachikawa and M. Shiga, J. Am. Chem. Soc., 127, 11908 (2005).
[6] K. Suzuki, M. Shiga, and M. Tachikawa, J. Chem. Phys. 129, 144310 (2008).
[7] J. R. Danielson, J. J. Gosselin, and C. M. Surko, Phys. Rev. Lett. 104, 233201 (2010).
[8] T. Yoshikawa, S. Sugawara, T. Takayanagi, M. Shiga, and M. Tachikawa, Chem. Phys. Lett., 496, 14 (2010).


Conducting Polyaniline  Polaronic vs. Bipolaronic Forms 
Jasmina Petrova, Julia Romanova, Galia Madjarova, Anela Ivanova, Alia Tadjer
University of Sofia, Faculty of Chemistry, 1 James Bourchier Ave., 1164 Sofia, Bulgaria 
Polyaniline (PANI) exists in several oxidation states, which allow a wide range of electric, magnetic and optical characteristics. Major attention receive the investigations searching for correlation between molecular geometry and electronic structure of the ground and excited states.
Our study is focused on the socalled emeraldine salt (ES) – the doped semioxidized form of PANI. Experimental data [1, 2] indicate that ES can exist both in spinsilent and in spinactive states. The electronic structure of ES is rationalized in terms of its bipolaron (diamagnetic) and polaron (paramagnetic) forms [3]. For describing these forms we constructed a series of fully HClprotonated oligomers (octamer to hexadecamer). The forms differ also in the position of the counterions (Cl^{}). All calculations include implicit aqueous environment.
The molecular features affected most prominently by the protonation, namely, structure, energetics, electron and spin density partitioning, are analyzed. The results show unequivocally that the studied molecular characteristics are essentially sizeindependent. The bipolarons and polarons are dissimilar both in geometry and in electron density distribution. Particularly, the negative ions are responsible for the localization of spin density at the nitrogens they screen, resulting in dissimilar spin lattices in the two fully polaronic forms [4].
Electronic spectra in aqueous medium are calculated. The simulated spectra are compared to the available experimental data.
[1] V. Prigodin, A. Samukhin, A. Epstein Synth. Metals 2004, 141, 155.
[2] P. K. Kahol, A. Raghunathan, B. J. McCormick Synth. Metals 2004, 140, 261.
[3] S. Stafström, J. L. Brédas, A. J. Epstein, H. S. Woo, D. B. Tanner, W. S. Huang, A. G. MacDiarmid Phys. Rev. Lett. 1987, 59, 1464.
[4] J. N. Petrova, J. R. Romanova, G. K. Madjarova, A. N. Ivanova, A. V. Tadjer. J. Phys. Chem. B 2011, 115, 3765.


Computational study of electronic structures of a characteristic [4Fe4S] cluster, [Fe_{4}S_{4}(SCH_{3})_{3}(CH_{3}COO)], in darkoperative protochlorophyllide oxidoreductase 
Yu Takano,^{1} Yasushige Yonezawa,^{1} Yuichi Fujita,^{2} Genji Kurisu,^{1} and Haruki Nakamura^{1}
^{1}Institute for Protein Research, Osaka University, Japan
^{2}Graduate School of Bioagricultural Sciences, Nagoya University, Japan 
The [4Fe4S] clusters play important roles in electron transfer and catalysis in ferredoxins and nitrogenases. Recently, a Xray structure of the darkoperative protochlorophyllide oxidoreductase (DPOR) has been determined at 2.3 Ĺ resolution [1]. The [4Fe4S] cluster in DPOR (NB cluster) has such a characteristic structural feature that one of the iron ions is chelated by the carboxylate group of Asp36, unlike conventional [4Fe4S] clusters coordinated with four Cys residues. To examine the effect of the Asp ligation on the enzymatic activities, three NBprotein mutants, D36C, D36S, and D36A, were prepared. Although the D36C and D36S substitutions almost nullified the activity, the D36A mutant exhibited 13 % of the wildtype level. The crystal structures of the D36C mutant was found to have the conventional [4Fe–4S] cluster coordinated with four Cys residues, while that of the D36A mutant had a [4Fe–4S] cluster chelated by three Cys residues and an unknown fourth nonprotein ligand, which was likely to be the hydroxide or chloride ion. These findings indicate that Asp ligation is important for the enzymatic activity.
In this study, we have investigated the electronic structure of the NB cluster to understand the role of the Asp ligation to the [4Fe–4S] cluster in the catalysis of DPOR using the density functional theory [2]. The electronic structure of the NB cluster is compared with those of the conventional [4Fe–4S] clusters in the D36C variant and the putative [4Fe–4S] clusters in the D36A mutant. Although the electronic structures are similar to each other, our computation shows that the redox potential of the NB cluster is lower than that of the D36C model in the 2–/3– reduction reaction, in an environment with the dielectric constant higher than 10, showing that the NB cluster can transfer an electron more easily than the conventional [4Fe–4S] cluster. This redox character demonstrates the important role of Asp36 in DPOR. It is also found that the electrondonating character of the [4Fe–4S] clusters in the 2–/3– reduction in an environment with high dielectric constant is in the same order as the experimental enzymatic activities of the wild type DPOR and its mutant, indicating that the fourth ligand of the [4Fe–4S] cluster in the D36A mutant is likely to be a chloride ion.
[1] N. Muraki, J. Nomata, K. Ebata, T. Mizoguchi, T. Shiba, H. Tamiaki, G. Kurisu, Y. Fujita, Nature 465 (2010) 110–114.
[2] Y. Takano, Y. Yonezawa, Y. Fujita, G. Kurisu, H. Nakamura, Chem. Phys. Lett. 503 (2011) 296–300. 

Towards Semiconductor GMR Devices: Tuning Interlayer Exchange Coupling of Magnetic Semiconductor Multilayers 
Z. Tang, F. Sun, B. Han, Z. Q. Zhu and J. H. Chu
Key Laboratory of Polar Materials and Devices, Ministry of Education,East China Normal University, Shanghai 200241, P. R. China 
Interlayer exchange coupling (IEC) plays an important role in manipulating transport properties of magnetic multilayers. It has demonstrated its technological impact in the form of metallic giant magnetoresistance (GMR) effect and has initiated the emergence of spintronics. Similarly, to fabricate semiconductor giant magnetoresistance devices, it is also essential to reversibly switch the interlayer exchange coupling of magnetic semiconductor multilayers between ferromagnetic and antiferromagnetic. However, after intensive studies since the late 80's, ones have realized that tuning the IEC in semiconductor multilayers is much more difficult than in metallic multilayers because either the antiferromagnetic IEC or the oscillatory IEC predicted by the conventional RKKY theory is usually absent in experiments.
In this work, firstprinciples calculations and an extended RKKY theory are employed to study the IEC in series model multilayers of diluted magnetic semiconductors. It is argued that the ferromagnetic IEC is an intrinsic characteristic of the magnetic semiconductor multilayers and to get the antiferromagnetic IEC, heavily doped spacer layers are essential. Based on the extended RKKY theory, we propose a prototype semiconductor giant magnetoresistance device consisting of Codoped TiO_{2}/VO_{2} diluted magnetic semiconductor multilayers, in which the reversibly tunable IEC is achievable via metalinsulator transition around 340 K. 

Chemistry at High Pressure 
John S. Tse
Department of Physics and Engineering Physics
University of Saskatchewan
Saskatoon, SK S7N 5E2, Canada

Pressure is a very sensitive parameter for the modification of the electronic structure of a material. In
this presentation, the theoretical perspective on how pressure can change the nature of the chemical
bond leading to novel magnetic, conducting and even superconducting properties will be presented and discussed through specific examples. The use of stateoftheart quantum mechanical calculations is crucial to the interpretation of the experimental observation. Comparison of the theoretical predictions and experiments will be illustrated with recent results.


Abinitio calculations of magnetic nanostructures

László Udvardi, László Balogh, László Szunyogh
Department of Theoretical Physics, Budapest University of Technology and Economics, Hungary 
As the magnetic storage devices approach a physical limit of a single atom the investigation of nanoclusters has become one of the important subjects in magnetism. Recent developments in nano technology permit to construct clusters with wellcontrolled structures and enable the measurement of various magnetic properties in atomic resolution. Abinitio calculations on magnetic nanostructures are necessary for a clear interpretation of experimental results and to attain full understanding of the underlying physical phenomena.
Our calculations are based on the local density approximation (LDA) of the density functional theory (DFT). The effective oneparticle problem is solved by means of the fully relativistic version of the KorringaKohnRostoker method using the multiple scattering formalism^{1}. For thin magnetic films surface Green's function technique has been applied to treat the semi infinite substrate and embeddedcluster Green's function method^{2} is used for the proper description of deposited magnetic clusters. In order to find the magnetic groundstate of nanoclusters and to analyse their stability
a new method is developed based on the gradients and second order derivatives of the band energy with respect of the transverse magnetization. The capability of the approach is demonstrated on a magnetic domain wall through a point contact.
Multiscale approaches are extremely useful tools to explore the magnetic properties of systems which would be too large to treat them with the standard methods of the density functional theory. In the most widely applied approximations the energy of a magnetic system is mapped onto a classical Heisenberg model. For the inclusion of relativistic effects such as the magnetic anisotropy and DzyaloshinskyMoriya interaction the scalar exchange coupling between the spins must be replaced by tensorial coupling and the model must be extended by terms responsible for the onsite anisotropy. In the framework of the multiple scattering theory the exchange interactions can easily be calculated by the torque method proposed by Liechtenstein^{3}. With the relativistic version of the torque method^{4} we are able to determine the full coupling tensor. By means of Monte Carlo simulations and atomistic spin dynamics complicated spinspiral ground state configuration which has been detected experimentally by spin polarized STM measurements^{5}
could be reproduced using the calculated exchange couplings.
[1] L Szunyogh and B Ujfalussy and P Weinberger and J Kollar, Phys. Rev. B, 49, 2721 (1994)
[2] Lazarovits, B. and Szunyogh, L. and Weinberger, P., Phys. Rev. B, 65, 104441 (2002)
[3] A. I. Liechtenstein and M. I. Katsnelson and V. P. Antropov and V. A. Gubanov, JMMM 67, 65 (1987)
[4] Udvardi, L. and Szunyogh, L. and Palotas, K. and Weinberger, P., Phys. Rev. B, 68, 104436 (2003)
[5] Bode, M. and Heide, M. and von Bergmann, K. and Ferriani, P. and Heinze, S. and Bihlmayer, G. and Kubetzka, A. and Pietzsch, O. and Bl\"ugel, S. and Wiesendanger, R., Nature 447, 190 (2007)


CCSD(T), MP2 and DFT investigations of Electron Affinities of Uracil: Microsolvation and the Polarized Continuum Model. 
M. Melichercik^{1}, L. F. Pasteka^{1}, P. Neogrady^{1} and M. Urban^{1,2}
^{1}Comenius University, Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences,
Mlynska dolina, 842 15 Bratislava, Slovakia.
^{2}Slovak University of Technology in Bratislava, Institute of Materials Science, Faculty of Materials Science and Technology in Trnava, Bottova 25, 917 24 Trnava, Slovakia. 
Electron affinities of Nucleic Acid Bases (NABs) are crucial for understanding the mechanism underlying the radiation damage to living tissues by lowenergy electrons, which can cause strand breaks in the DNA duplex. There is a clear evidence that the environment contributes to the stability of the valence bound uracil anion significantly [14]. Recently, we presented [5] reference CCSD(T) calculations of the adiabatic electron affinities (AEA) and the vertical detachment energies (VDE) of the free and the microhydrated uracil•(H_{2}O)_{n} (n=13). The OVOS technique was used to alleviate large computer demands of CCSD(T) calculations [4,5]. Next, we have extended our AEA and VDE studies to DFTB3LYP and UMP2 calculations of microhydrated uracil•(H_{2}O)_{n} (n=15) complexes treated at the same time by a polarized continuum model (PCM) [6]. Due to the microsolvation AEAs and VDEs increase by 600660 meV, and by more than 1100 meV, respectively, for U(H_{2}O)_{5} complexes. With increasing dielectric constant in the PCM model AEAs attained the value of 2000 – 2200 meV and VDEs the value of 2700 – 3000 meV. Electron affinities depend on specific structural features of the microsolvated U(H_{2}O)_{n} complexes.
DFT data for AEAs of microsolvated uracil copy trends of benchmark CCSD(T) results being systematically by 200 – 230 meV higher than CCSD(T) values depending on the particular structure of the complex. MP2 values are underestimated. Although DFTB3LYP electron affinities differ from benchmark CCSD(T) data significantly, all trends are reproduced reasonably accurately. This gives a support for using DFT in investigations of trends in larger molecules and their complexes. More accurate values can be obtained by tuning DFT by benchmark CCSD(T) results.
This work was supported by the Slovak Research and Development Agency APVV (Contract No. LPP015509) and VEGA1/0520/10.
References:
[1] Kim S., Schaefer H. F., J. Chem. Phys 125, 144305 (2006).
[2] Eustis S., Wang D., Lyapustina S., Bowen K. H. J. Chem. Phys. 127, 224309 (2007).
[3] Brancato G., Rega N., Barone V. Chem. Phys. Lett. 500, 104 (2010).
[4] Dedíková P., Demovič L., Pitoňák M., Neogrády P., Urban, M. Chem. Phys. Lett. 481, 107 (2009).
[5] Dedíková P., Neogrády P., Urban M. J. Phys. Chem. A 115, 2350 (2011).
[6] Cossi M., Barone V., Mennucci B., Tomasi J. Chem. Phys. Lett. 286, 253 (1998); Tomasi J., Mennucci B., Cammi R. Chem. Rev. 105, 2999 (2005) 

FRANCKCONDON FACTORS FOR DIATOMIC MOLECULES FOR AN ARBITRARY ANHARMONIC POTENTIAL 
L. Sandoval*, I. Urdaneta and A. Palma
*Facultad de Ciencias de la Computacion, Benemerita Universidad Autonoma
de Puebla. Puebla, Pue. 72570, Mexico
Instituto de Fisica, Benemerita Universidad Autonoma de Puebla. Puebla, Pue. 72570, Mexico 
In this work we develop a harmonic approximation of the FranckCondon Factors (FCF) for any anharmonic potential of diatomic molecules.
The method is based on the Taylor series expansion of the potential and the second quantization formalism. Well known recurrence relations are used to calculate the FCF, which are incorporated in the hamiltonian. Keeping then only the quadratic terms, by the BogoliubovTyablikov transformation the hamiltonian is found to be equivalent to an harmonic oscillator. The derivation is an alternative route to the Iterative Bogoliubov transformation (IBT), widely used to treat anharmonic potentials in a nonperturbative way. The FCF obtained by our method for the Morse potential are compared with numerical techniques like the RKR method and the Morse itself. Our results are in agreement with these numerical methods, being our technique entirely analytical and much simpler to use. 

Universal product angularmomentum distributions in photodissociation
and reaction collisions 
O. S. Vasyutinskii
Ioffe Institute, Russian Academy of Sciences, 194021 St Petersburg, Russia 
The field of stereodynamics and vector correlations in chemical and photochemical reactions
attracts much attention since decades. The importance of the vector properties in the reactions is based on the fact that practically all interactions within a reaction complex are intrinsically
anisotropic which in many cases results in the electronic and nuclear motion anisotropy in the reaction products. The talk reviews recent results on the full quantum mechanical treatment of the spin and orbital angular momentum recoil angle distributions of the products of chemical and photochemical reactions in diatomic and polyatomic molecules. The distributions obtained are presented in the body frame and in the molecular frame using the spherical tensor formalism. The main result is that the recoil angle distribution can be written, irrespective of the reaction mechanism, in a universal form in terms of the anisotropytransforming coefficients K_{q}K_{ii} c which contain all the information regarding the reaction dynamics, and can be either directly determined from experiment or calculated from theory.
The coefficients are scalar values which depend on the photofragment state multipole rank ( K), on the initial reagent spherical tensor rank ( K_{i}), and on component q_{i} of the ranks K and K_{i} projected onto the recoil direction k. An important new conservation rule is revealed through the analysis, namely that the component q_{i} is preserved in any scattering, or photolysis reaction. The coefficients K_{q}K_{ii} c act as transformation coefficients between the angular momentum anisotropy of the reactants and that of the product. The results obtained are generalized to the case where the reaction reagents possess spin, or orbital electronic angular momentum polarization. General expressions for the anisotropytransforming coefficients beyond the axial recoil limit contain scattering Smatrix elements and take into account all possible types of nonadiabatic interactions in the reaction complex, as well as the full range of possible coherence effects. Many important particular cases of these expressions are discussed. They are: (a) the role of Coriolis interactions in the photolysis of linear molecules which result is the molecular helicity nonconservation; (b) quasiclassical approximation of the molecular scattering function in the high J limit. The talk also reviews recent experimental results on the photodissociation of a number of polyatomic molecules, and shows how the investigation of the values determined for the speeddependent parameter â and higherrank anisotropy parameters supported the interpretation of the photodissociation dynamics.
.
References
[1] V. V. Kuznetsov and O. S. Vasyutinskii, J. Chem. Phys. 123, 034307 (2005).
[2] V. V. Kuznetsov and O. S. Vasyutinskii, J. Chem. Phys. 127, 044308 (2007).
[3] V. V. Kuznetsov, P. S. Shternin, O. S. Vasyutinskii, Phys. Scripta, 80, 048107 (2009)
[4] A. G. Smolin, O. S. Vasyutinskii, A..J. OrrEwing, Mol. Phys. 105, 885 (2007)
[5] P. S. Shternin and O.S. Vasyutinskii, J. Chem. Phys. 128, 194314 (2008).
[6] A. G. Suits and O. S. Vasyutinskii, Chem. Rev. 106, 3706 (2008).
[7] V. V. Kuznetsov, P. S. Shternin, O. S. Vasyutinskii, J. Chem. Phys., 130, 134312 (2009).
[8] G. G. BalintKurti and O. S. Vasyutinskii, J. Phys. Chem. A, 113, 14281 (2009).


Quantum Chemistry on Quantum Computers 
L. Veis and J. Pittner
J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Prague, Czech Republic 
Quantum computers are appealing for their ability to solve some tasks much faster than their classical counterparts, e.g. efficiently factore integers. Quantum chemistry could in principle benefit from them as well, for example by an efficient solution of manybody Hamiltonian eigenvalue problem [1]. As was shown in the seminal work by AspuruGuzik et. al. [2], quantum computers, if available, would be able to perform the full configuration interaction (FCI) energy calculations with only a polynomial scaling, in contrast to conventional computers where FCI scales exponentially.
We have developed a code for simulation of quantum computers and implemented our version of the quantum full configuration interaction (QFCI) method which uses the iterative phase estimation algorithm. This approach reduces demands on the total number of quantum bits (qubits) as only one is needed in the readout part of the quantum register and the whole algorithm proceeds in an iterative manner.
We have tested its performance and applicability for nonrelativistic as well as relativistic CI energy calculations. Nonrelativistic QFCI calculations of the four lowest lying electronic states of methylene molecule (CH_{2}), which exhibit a multireference character were performed [3]. It has been shown that with a suitably chosen initial state of the quantum register, one is able to achieve the probability amplification regime of the iterative phase estimation even for nearly dissociated molecule. Relativistic Kramersrestricted CI calculations employing the QFCI algorithm have been applied to the spinorbit coupling in the SbH molecule [4]. We have also designed the quantum circuits for the simplest proofofprinciple physical realizations of relativistic quantum chemical computations on quantum computers.
[1] Abrams, D. S.; Lloyd, S. Phys.Rev.Lett. 1999, 83, 5162–5165.
[2] AspuruGuzik, A.; Dutoi, A. D.; Love, P. J.; HeadGordon, M. Science 2005, 309, 1704–1707.
[3] Veis, L.; Pittner, J. J. Chem. Phys. 2010, 133, 194106.
[4] Veis, L; Višnák, J.; Fleig, T.; Knecht, S.; Saue, T.; Visscher, L.; Pittner, J. in preparation


Hydrogen Bond Dynamics and Computational Vibrational Spectroscopy in Aqueous Solution: The Case Study of Histamine Monocation 
Robert Vianello, Janez Mavri
National Institute of Chemistry, Hajdrihova 19, SI–1000 Ljubljana, Slovenia. Email: vianello@irb.hr 
Histamine is a biogenic amine playing important roles in molecular biology and medicine, which under physiological conditions assumes the monocationic form (Figure 1). It participates in complex processes related to intercellular communication, defence and cell proliferation in mammals. Its signalling pathways are involved in conditions such as depression, schizophrenia and Alzheimer's disease. Consequently, processes involving histamine transport and binding to macromolecules through hydrogen bonding have a significant biological relevance.
The nature of interactions of histamine with solvent water molecules is experimentally reflected in the N–H vibrational stretching frequencies. Assignment of the experimental spectra^{[1]} (Figure 2) reveals a broad feature between 3350 and 2300 cm^{–1}, which includes a mixed contribution from the ring and the aminoethyl N–H stretching vibrations.
Computational analysis^{[1]} was performed by applying an a posteriori quantization of particular nuclear motions to snapshot structures obtained after Car–Parrinello MD simulations (Figure 3). It showed that the ring amino group absorbs at higher frequencies than the remaining three amino N–H protons. In this way, these results complemented the experiment that cannot distinguish between the two sets of protons. The effects of deuteration were also considered. Calculated spectra are in very good agreement with the experiment. The presented methodology is of general applicability to strongly correlated systems and it is particularly tuned to provide computational support to vibrational spectroscopy.



Figure 1. The structure of the histamine monocation.

Figure 2. Experimental vibrational spectra of histamine monocation recorded in H_{2}O (left) and in D_{2}O (right).

Figure 3. Calculated N–H (full black line) and N–D (dashed black line) stretching envelopes, arising from free–amino (red lines) and ring amino (blue lines) groups.

^{[1]} J. Stare, J. Mavri, J. Grdadolnik, J. Zidar, Z. B. Maksić, R. Vianello, J. Phys. Chem. B 2011, 115(19), pp59996010. 

Relativistic coupled cluster methods: benchmark applications for heavy element chemistry 
Lucas Visscher
Amsterdam Center for Multiscale Modeling
VU University Amsterdam 
Molecular complexes of the heaviest transition metals are interesting due to their applications in catalysis and nanostructured materials. For understanding details of the associated reaction mechanisms and analyzing spectroscopic observations it is therefore desirable to develop quantum chemical methods that can provide estimates of reaction barriers and excitation energies with quantitative accuracy. This demands a rigorous treatment of both relativistic and electron correlation effects. With the advent of eXact 2Component (X2C) relativistic methods[1], allelectron treatments that include both scalar relativistic effects and spinorbit coupling effects from the outset have become much more practical, leaving the electroncorrelation stage of the calculation as the rate determining step.
By treating some recent applications[2] of relativistic coupledcluster theory[3] I will discuss the current status of these techniques[4] in comparison with other methods like multireference perturbation theory, multireference configuration interaction and density functional theory. I will focus on excitation energies but also discuss the application of relativistic electronic structure methods to molecular properties, in particular those properties that are strongly influenced by relativistic effects such as nuclear quadrupole coupling constants, NMR shieldings and Mössbauer istope shifts
[1] K. Dyall, J. Chem. Phys. 106 (1997) 9618. M. Iliaš, H. J. A. Jensen, V. Kellö, B. O. Roos, and M. Urban, Chem. Phys. Lett. 408 (2005) 210. W. Kutzelnigg and W. Liu, J. Chem. Phys. 123 (2005) 241102. M. Filatov, J. Chem. Phys. 125 (2006) 107101. W. Kutzelnigg and W. Liu, J. Chem. Phys. 125 (2006) 107102. M. Iliaš and T. Saue, J. Chem. Phys. 126 (2007) 064102. J. Sikkema, L. Visscher,T. Saue, M. Iliaš, J. Chem. Phys. 131 (2009) 124116.
[2] L. Belpassi et al. J. Chem. Phys. 126 (2007) 064314. A. S. P. Gomes et al. J. Chem. Phys. 133 (2010), 064305. R. L. A. Haiduke, A. B. F. Da Silva, L. Visscher Chem. Phys. Lett. 445 (2007) 95. S. Knecht et al., Theor. Chem. Acc. (2011) 631. F. Réal, A. S. P. Gomes, L. Visscher, V. Vallet, E. Eliav, J. Phys. Chem. A 113 (2009) 12504. P. Tecmer, A. S. P. Gomes, U. Ekstrom, L. Visscher, PCCP 13 (2011) 6249.
[3] L. Visscher, T. Lee, and K. Dyall, J. Chem. Phys. 105 (1996) 8769; L. Visscher, E. Eliav, and U. Kaldor, J. Chem. Phys. 115, (2001) 9720; H. S. Nataraj, M. Kallay, and L. Visscher, J. Chem. Phys. 133 (2010) 234109 .
[4] DIRAC, a relativistic ab initio electronic structure program, Release DIRAC10 (2010), written by T. Saue, L. Visscher and H. J. Aa. Jensen, with new contributions from R. Bast, K. G. Dyall, U. Ekström, E. Eliav, T. Enevoldsen, T. Fleig, A. S. P. Gomes, J. Henriksson, M. Iliaš, Ch. R. Jacob, S. Knecht, H. S. Nataraj, P. Norman, J. Olsen, M. Pernpointner, K. Ruud, B. Schimmelpfennnig, J. Sikkema, A. Thorvaldsen, J. Thyssen, S. Villaume, and S. Yamamoto (see http://dirac.chem.vu.nl).


Functional Derivatives and Differentiability in DensityFunctional Theory 
Yan Alexander Wang
Department of Chemistry, University of British Columbia, Vancouver, BC V6T 1Z1, Canada 
Based on Lindgren and Salomonson’s analysis on Fréchet differentiability [ Phys. Rev. A 67, 056501 (2003)], we showed a specific variational path along which the Fréchet derivative of the LevyLieb functional does not exist in the unnormalized density domain. This conclusion still holds even when the density is restricted within a normalized space. Furthermore, we extended our analysis to the Lieb functional and demonstrated that the Lieb functional is not Fréchet differentiable. Along our proposed variational path, the Gâteaux derivative of the LevyLieb functional or the Lieb functional takes a different form from the corresponding one along other more conventional variational paths. This fact prompted us to define a new class of unconventional density variations and inspired us to present a modified density variation domain to eliminate the problems associated with such unconventional density variations. 

Determining the structure of dialdehyde functionalised cellulose nanocrystals using semiempirical molecular modelling 
Thomas Morgan, Theo van de Ven and M. A. Whitehead
Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, QC, H3A 2K6, Canada 
The crystalline structure of cellulose is studied using Semi Empirical Molecular Modelling. Hydrogen bonding is found to hold the cellulose chains together in each plane of the crystal while the separate planes of cellulose are found to stack on top of each other in a staggered fashion. Dialdehyde functionalised cellulose is examined and the structure is found to be less crystalline than unmodified cellulose with fewer hydrogen bonds between the chains. The mechanism for the periodate oxidation of cellulose is studied.


Figure 1. Single layer dialdehyde modified cellulose.

Figure 2. Single layer dialdehyde modified cellulose showing DLMOs. H bond circled in black.



Density Functionals for Transition Metal Species 
Wanyi Jiang, Marie Laury, Sammer Tekarli, and Angela K. Wilson
Department of Chemistry and Center for Advanced Scientific Computing and Modeling
University of North Texas

Density functional theory is often the method of choice for transition metal calculations, due to its computational cost and success in providing insight about numerous chemical problems. Despite the reputed successes, the determination of the “best” functional to use in calculations is still not necessarily obvious. To assess the appropriateness of various density functionals for transition metal systems, comprehensive studies of a large number of functionals and a large, diverse representation of transition metals are necessary. Unfortunately, prior studies have largely focused upon a small set of functionals or a relatively limited set of molecules, and the "best" functional, overall, has not been consistent from one study to the next. We present an extensive study of over 50 functionals, and nearly 200 3d transition metal species. 

TDDFT studies on electronic excitations and hyperpolarizabilities of transitionmetal containing compounds 
Kechen WU
State Key Laboratory of Structural Chemistry, Laboratory of Theoretical and Computational Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian 350002, China 
We present the recent advances in the computational studies on the secondorder nonilinear optical properties of coordination transitionmetal containing compounds within timedependent density functional theory. The study revealed that the metalmetal interactions existing in the coordinated polynuclear compounds make significant contributions to the secondorder responses. The charge transfer process originated from the d1d2 transitions has been identified to be one of the effective mechanisms for the secondorder response in these kind of compounds. The study indicates that inorganic polynuclear transitionmetal clusters could be the promising midtofar nonlinear optical materials and molecular devices due to the distinctive metaltometal chargetransfer character, optical transparency in IR region, diverse structural configurations and flexible coordinated organic/inorganic ligands. A series of potential IRactive secondorder nonlinear optical transitionmetal containing cluster compoumds are reproted. The study may benefit to the efforts that we have made in searching novel midtofar infrared nonlinear optical materials and molecular devices. 

Towards reliable density functional approaches for manganese complexes 
Shusuke Yamanaka,^{1} Keita Kanda,^{1} Toru Saito,^{1} Yasutaka Kitagawa,^{1}
Takashi Kawakami,^{1} Masahiro Ehara,^{2} Mitsutaka Okumura,^{1}
Haruki Nakamura,^{3} Kizashi Yamaguchi^{4}
^{1}Graduate School of Science, Osaka University, Japan
^{2}Institute for Molecular Science, Japan
^{3}Protein Institute, Osaka University, Japan
^{4}TOYOTA Physical & Chemical Research Institute, Japan,

I. Introduction
Recently we have investigated a manganese cluster, a model for the oxygen evolving complex (OEC) in photosytem II [1], which catalyze the decomposition reaction of water. We rely on the newest and most reliable Xray structure [2] and the optimized ones starting from the Xray structure. However the stable spin states for some of them calculated by the B3LYP method are not consistent with the EPR experimental results of the native cluster [1]. We are now examining the modeling structure including various protonation types to the oxygens inandaround the cluster. It is also possible that the B3LYP does yield incorrect magnetism of the manganese cluster. To confirm this, we implement a benchmark test of B3LYP, as well as other functionals, for calculations of magnetism of various manganese complexes [3].
II. Results
For a test set, we choose dinuclear manganese complexes, for which the Xray diffraction structure and the magnetic interaction have been experimentally reported. It includes various manganese complexes with oxidation patterns as follows: Mn(II)_{2} Mn(II)Mn(III), Mn(III)_{2}, Mn(III)Mn(IV), and Mn(IV)_{2}. First, starting from triplezeta plus diffuse and polarization function quality, we pruned the basis set step by step with monitoring computational results of magnetic interactions using B3LYP functional, deciding a modest but reliable basis set. With employing the basis set, we examined various exchangecorrelation functionals, BHandHLYP, CAMB3LYP, TPSSh, PBE0, PBEh35, HSEh1PBE, HSE1PBE, HSE2PBE, LCwPBE, M06, M062X, M06HF, HF, B3LYP*, for calculations of magnetism. The computational results will be discussed in relation to the experimental results. In particular we focus our attention on the effects of protonation to bridged oxygens and changes of oxidation states on the magnetic interactions, which will be a guideline principle to inspect the protonation modes of states in the Kok cycle of OEC.
References
[1] K. Kanda et al. CPL 506 (2011) 98; S. Yamanaka, et al. CPL 511(2011)138; K. Kanda et al. Polyhedron in press; S. Yamanaka et al. Adv Quantum Chem, submitted.
[2] Y. Umena, K. Kawakami, JR. Shen, N. Kamiya, Nature 473 (2011) 55.
[3] S. Yamanaka et al., in preparations.


A new molecular orbital theory in affine space 
Jun Yasui
Frontier Research Center, Canon Inc.
302, Shimomaruko 3chome, Ohtaku, Tokyo 1468501, Japan 
A new method of molecular orbital calculation that includes molecular structures and orbital exponents of basis set functions not as parameters but as variables has been developed [1]. This method uses STO molecular integrals expressed in polynomials with respect to the new variables. The HartreeFockRoothaan equation is modified with additional conditions such as the cusp condition, the virial condition, and other conditions that should be satisfied for the Schrödinger equation. The new molecular equation is a simultaneous polynomial equation in affine space having equivalent variables such as molecular structures, molecular orbital coefficients, and orbital exponents of STO. The present method has a possibility to change the way of research in molecular science, for example, we may be able to obtain symbolic functional expressions of the electronic states with respect to the molecular structures and the orbital exponents of basis set functions.
Reference
[1] J.Yasui, to be published in Progress in Theoretical Chemistry and Physics as a selected paper in Internatinal Conference on DVXα Method Aug. 2010 in Kerea, Springer this summer.


Antidot Structure Dependences of Openshell Characters and Aromaticities for Hexagonal Graphene Nanoflakes 
Kyohei Yoneda,^{1} Yudai Inoue,^{1} Tomoya Inui,^{1} Yasuteru Shigeta,^{1} Takashi Kubo,^{2} Benoît Champagne^{3} and Masayoshi Nakano^{1}
^{1}Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Japan
^{2}Department of Chemistry, Graduate School of Science, Osaka University, Japan
^{3}Laboratoire de Chimie Théorique (LCT), Facultés Universitaires NotreDame de la Paix (FUNDP), BELGIUM 
The openshell singlet state of graphene nanoflakes is at the origin of their unique physicochemical properties. In this study, we theoretically investigate the openshell characters and aromaticities of hexagonal graphene nanoflakes with different sizes of antidot structures, using the longrange corrected spinunrestricted density functional theory, LCUBLYP, method. It is found that the openshell character exhibits an oscillatory behavior with increasing the size of the antidot structure, and the nucleusindependent chemical shift (NICS) – an index of aromaticity – also depends on the openshell character. These antidot structure dependences are rationalized in terms of the variations in the HOMO–LUMO energy gaps, which is explained by the molecular orbital correlation diagram. 

Representation of structureproperty relationships in polymorphic systems 
Koretaka Yuge
Department of Materials Science and Engineering, Kyoto University, Kyoto 6068501, Japan 
While structureproperty relationships in crystals are fundamental prerequisite to design and optimize desirable materials, quantitative assessment for the relationships has been just beginning. Cluster expansion (CE) is one of the most successful approach based on abinitio calculation to predict configurational scalar as well as tensor properties such as internal energy, bandgap, density of states, and elasticity. However, application of the current CE is essentially limited to the single lattice, which makes it really difficult to applying to the polymorphic systems.
Here we introduce variable lattice CE (VLCE)[1] enabling to treat multiple structures in a single Hamiltonian, which overcomes the limitation in CE. We demonstrate derivation, concept, and interpretation of the proposed VLCE, and show application to 2dimensional system to search groundstate structure in polymorphs.
References
[1] K. Yuge, J. Phys.: Condens. Matter 22, 125402 (2010).


Use of onerange addition theorems in evaluation of multicenter electric field integrals of Slater type orbitals and Yukawalike interaction potential 
Nimet ZAIM
Department of Physics, Faculty of Sciences, Trakya University, Edirne, Turkey 
The calculation is performed for multicenter electric field integrals containing Slater type orbitals and Yukawalike interaction potential using their onerange addition theorems established in Ref.[1] with the help of complete orthonormal sets of ψ^{α} exponantial type orbitals (α=1,0,1,2,…) [2]. The results of computer calculations are presented. The convergences of the series is tested by calculating concrete cases for the arbitrary values of quantum numbers, orbital parameters and internuclear distances.
[1] I. I. Guseinov, Bull. Chem. Soc. Jpn., 78 (2005) 611
[2] I. I. Guseinov, Int. J. Quantum Chem. ,90 (2002) 114


Mndoped Thiolated Au_{25} Nanoclusters: Atomic Confguration, Magnetic Properties, and A Possible Highperformance Spin Filter 
M. Zhou,^{1} Y. Q. Cai,^{1} M. G. Zeng,^{1} C. Zhang,^{1,2} and Y. P. Feng^{1}
^{1}Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore, 117542
^{2}Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 
We report an ab inito investigation on the groundstate atomic configuration, electronic structures, magnetic and spindependent transport properties of Mndoped Au_{25} nanoclusters protected by thiolate. It is found that the most stable dopant sites are near surfaces, rather than the center position of the nanoparticles. Transport calculations show that highperformance spin filters can be achieved by sandwiching these doped clusters between two nonmagnetic Au electrodes. The nearly perfect spin filtering ori g! inates from localized magnetic moments of these clusters that are well protected by ligands from the presence of electrodes 

