XVIth International Workshop on
Quantum Systems in
Chemistry and Physics
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Unraveling nanoparticle properties using density functional theory
Christine M. Aikens
Kansas State University, Manhattan, KS 66506, USA
Theoretical investigations of monolayer-protected 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. Time-dependent density functional theory (TDDFT) is employed to examine the spectrum of the Au25(SR)18- nanoparticle, and it is determined that delocalized orbitals in the 13-atom nanoparticle core are primarily responsible for the excited state transitions. The ligand field arising from the surrounding gold-thiolate 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 Au11(BINAP)4Cl2+ system provide important information regarding ligand effects on core structure and the resulting circular dichroism spectra. The low energy peaks of Au11L4X2+ 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 C1 geometry, the lowest energy structure of Au11L4X2+ has a chiral C2 structure. The chiral core of Au11L4X2+ 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” Au38(SR)24 nanocluster is shown to be chiral with D3 symmetry. Au38(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 Au25(SR)18, delocalized superatom-like orbitals are responsible for its properties.
First-Principles Calculations of Hydrogen Impurities in Graphenes and Carbon Nanotubes
Mohammad Shafiul Alam,1 Nyayu Siti Nurainun,1,2 Fahdzi Muttaqien,1,2 Agung Setiadi1,2 and Mineo Saito1,3
1Division of Mathematical and Physical Sciences, Graduate School of Natural Science and Technology,Kanazawa University, Kakuma Kanazawa 920-1192, Japan
2Department of Computational Science, Bandung Institute of Technology, Indonesia
3Collaborative Research Center for Frontier Simulation Software for Industrial Science, Institute of Industrial Science, University of Tokyo, 4-6-1 Komaba, Meguroku Tokyo 153-8505, Japan
Carbon Nanomaterials have attracted much attention since they are candidates for post-silicon materials. Since hydrogen is a common impurity in graphene [1-3] 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 mono-hydrogen in graphene, CNT (5,5) and CNT (10,0). We perform spin-polarized generalized gradient approximation by using first-principles calculations. In the most stable structure of mono-hydrogen, 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 Å, 1.12 Å and 1.12 Å for graphene, CNT (5,5) and CNT (10,0), respectively. These bond lengths are close to that in a CH4 molecule (1.09 Å), which is typical for sp3 C-H bond lengths. In these three cases [Fig. 1] the spin polarized states are found to be most stable and the magnetic moments are 1 μB.

[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, 225502-1 (2004).

Figure 1. Spin densities of the mono-hydrogen 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 half-life 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. Richardson1 and Stuart C. Althorpe1
1 Department of Chemistry, University of Cambridge, UK
This talk will explain how semi-classical instanton theory can be formulated very simply in terms of ring-polymers1-3. 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 tunneling-splitting patterns. The approach is readily applied to multi-dimensional systems, including condensed-phase systems with the application of periodic boundary conditions. We describe calculations of tunneling-splitting 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 origin-dependent expressions for the material constants, and thus do not correspond to
physically acceptable observable quantities. There is therefore a need for origin-independent definitions of the material constants.
Origin-independent 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, origin-independent 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 well-known 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 long-range behaviors
Juan Carlos Angulo
Departamento de Fisica Atomica, Molecular y Nuclear, and Instituto Carlos I de Fisica Teorica y Computacional, Universidad de Granada, E-18071 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 one-particle densities in both conjugated spaces, and neutral–cation similarity in ionization processes are analyzed. The results are interpreted attending to shell-filling patterns, and also in terms of experimentally accessible quantities of relevance in ionization processes.
Comments on the cross-coupling reaction
Shigeyuki AONO
Kanazawa University, Kanazawa, Japan

E-mail address: aonosan2000@ybb.ne.jp
Suzuki and Negishi have investigated the method of cross-coupling 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 Woodward-Hoffmann. 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 ( qij). For butadiene, C4 chain, q14 is obtained negative which suggests the 1-4 sites are repulsive implying the ring closure between them never occurs. On the other hand q16 in the C6 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 d-metal connects two C2 molecule (ethylene). The d-orbital is regarded as two p-orbitals, dxz and dyz (called 3 and 4-th). Each ethylene connects the metal to form pz 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 C4 chain, butadiene. Start from C6 ring, say benzene ring. We have now the ring, then the vertex is pointed 1. We evaluate the bond order q13 vanishing. We now find the 1-3 bond is non-bonding. If any perturbation happens, this bond is breaking and the metal being separates. Our purpose is completed.
Non-adiabatic effects in the action of radiation on molecular systems
Marie-Christine Bacchus-Montabonel
Laboratoire de Spectrométrie Ionique et Moléculaire, CNRS et Université Lyon I, 43 Bd. Du 11 Novembre 1918, 69622 Villeurbanne Cedex, France, bacchus@lasim.univ-lyon1.fr
Non-adiabatic 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 non-adiabatic methods based on wave packet propagation to calculate cross sections and rate constants in ion-atom 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 C-Cl and C-Br bonds in bromoacetyl chloride Br-CH2-COCl photodissociation [3]. In such a process, non-adiabatic effects induce a trapping of the system before dissociation leading thus preferentially to C-Cl breaking, although the C-Br 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 non-adiabatic interaction around avoided crossings between the different entry and exit channels [6].


1.N. Vaeck, M.C. Bacchus-Montabonel, E. Baloïtcha, M. Desouter-Lecomte, Phys. Rev. A 63, 042704 (2001).
2.D. Lauvergnat and A. Nauts, J. Chem. Phys. 116, 8560 (2002).
3.B. Lasorne, M.C. Bacchus-Montabonel, N. Vaeck, M. Desouter-Lecomte, J. Chem. Phys. 120, 1271 (2004).
4.B.D. Michael, P.D. O'Neill, Science 287, 1603 (2000).
5.M.C. Bacchus-Montabonel and Y.S. Tergiman, Chem. Phys. Lett (2011) (in press)
6.E. Rozsályi, E. Bene, G.J. Halász, Á. Vibók, M.C. Bacchus-Montabonel, Phys. Rev. A 81, 062711 (2010).
Electronic Absorption Spectra of the RgAr (Rg=Cs, Rb) Van der Waals Complexes
J. Dhiflaouia, H. Berrichea,b and M. C. Heavenc
aLaboratoire de Physique et Chimie des Interfaces, Département de Physique, Facultée des Sciences de Monastir, Avenue de l’Environnement, 5019 Monastir, Tunisie)
bPhysics Department, Faculty of Science, King Khalid University, P. O. Box 9004,
Abha, Saudi Arabia.
cChemistry Department, Emory University, Atlanta, USA

*E-mail 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 [e-Ar] 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 core-core 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 X2Σ+---A2Π1/2, X2Σ+---A2Π3/2 and X2Σ+--B2Σ1/2+absorption spectra.
The potential energy surface of Li2+(X2Σg+) alkali dimer colliding with the Xe atom
S. Saidi1, C. Ghanmi1, F. Hassen2 and H. Berriche*1,3
1Laboratoire de Physique et Chimie des Interfaces, Département de Physique, Faculté des Sciences de Monastir, Avenue de l’Environnement, 5019 Monastir, Tunisia.
2Laboratoire de Physique des Semiconducteurs et des Composants Electroniques, Faculté des Sciences, Avenue de l’environnement, 5019 Monastir, Tunisie
3Physics 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 Li2+(X2Σg+) alkali dimer and the Xenon atom have been calculated for the equilibrium distance of the Li2+(X2Σg+) and for an extensive range of the two Jacobi coordinates, R and γ. We have used an ab initio approach based on non-empirical pseudopotential and a parametrized l-dependent polarization potential [1]. The core-core 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 Li2+(X2Σg+)-Xe system to only one active electron. The Three-Body 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 Li2+(X2Σg+) 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 Li2+ ionic alkali molecule in Xenon small clusters.

[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 Li2+(X2Σg+) in small Xen clusters: structure and stability
S. Saidia, C. Ghanmia, F. Hassenb and H. Berriche*a,c
aLaboratoire de Physique et Chimie des Interfaces, Faculté des sciences, Université de de Monastir, Avenue de l’Environnement, 5019 Monastir, Tunisie
bLaboratoire de Physique des Semiconducteurs et des Composants Electroniques, Faculté des Sciences, Avenue de l’environnement, 5019 Monastir, Tunisie
cPhysics Department, College of Science, King Khalid University, P. O. B. 9004, Abha, Saudi Arabia

*E-mail address: hamidberriche@yahoo.fr
The structure and geometries of the small Li2+(X2Σg+)Xen clusters taken in different geometries with special symmetry groups, are examined. A one-electron pseudopotential approach is used to generate the potential energy surface of the Li2+-Xe triatomic system for a fixed distance between the two Li alkali atoms (the Li2+ equilibrium distance) and for different angles and distances between the Xenon and the Li2+ center of mass. In this approach, the effect of the Li+ core and the electron-Xe 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 Li2+Xe interactions are introduced using an analytical form to describe the collision between the alkali ionic dimer and the Xe atom. However, a Lennard-Jones form is used for the Xe-Xe interactions and then included in the total potential energy surface describing the Li2+-Xen cluster. The optimized and stable geometries are performed using the Monte-Carlo 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 Li2+ dimer.

Key words: Pseudopotential, Microsolvation of clusters, Monte-Carlo, Structure,
Spin states in Transition Metal Compounds
A.M. Pradipto1, R. Maurice2,3, A. Rudavskyi1,
Nathalie Guihéry2, C. de Graaf 1,3,4 C. Sousa5, and R. Broer1

1Zernike Institute for Advanced Materials, University of Groningen, The Netherlands
2Laboratoire de Chimie et Physique Quantiques, Université de Toulouse 3, France
3Departament de Quimica Fisica i Inorganica, Universitat Rovira i Virgili, Tarragona, Spain
4Institucio Catalana de Recerca i Estudis Avancats (ICREA), Barcelona, Spain
5Dept. 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 co-exist
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, spin-orbit 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 magneto-electric 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, 3092-3101.
Examining the Limits of Physical Theory:
Analytical Principles and Logical Implications
Erkki J. Brändas
Department of Physical and Analytical Chemistry
Quantum Chemistr
Uppsala University
SE-751 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 long-established 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 macro-world 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 non-conventional time evolution including the emergence of Jordan blocks in the propagator, which leads to the origin of so-called coherent dissipative structures derived via uniquely defined spatio-temporal 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 back-ground dependent features of both special and general relativity theory.
Coupled-cluster methods for molecular solutes described with the framework of the Polarizable Continuum Model.
Roberto Cammi
Dipartimento di Chimica, Università 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 ab-initio QM description of the solute, the procedure is based on the definition of an effective Hamiltonian which contains a solute-solvent interaction operator of integral type with a two body kernel. The corresponding effective Schroedinger equation is non-linear and its solution requires a suitable generalization of the standard procedures of ab-initio calculation in gas-phase.
Within the several version of continuous solvation model, the Polarizable Continuum Model of Tomasi and co-worker [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 ab-initio coupled-cluster level [3-7]. 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 SAC-CI and EOM-CC approaches,
3.the linear response functions for the evaluation of dynamical properties of molecular solutes.

[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 São Paulo, São Paulo, Brazil
The cobalt-corrin 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 Co-C 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 alpha-betha bands between 460-560 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.
[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 Plane-Wave 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’), (kg|k’g’) and (kg|g’g’’), where k symbols stand for plane-wave functions and g’s are gaussians. Fűsti-Molnár and Pulay1 came with an idea that the use of mixed plane-wave 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 achieved2 in efficient evaluation of Coulomb integrals (kk’|gg’) in electron scattering theory may also be profitable for the mainstream quantum chemistry.

1. L. Fűsti-Molnár, 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 Self-Assembled pi–pi Stacks of Perylene Diimide Dyes
Julien idé1, Frédéric Castet1, Raphaël Méreau1, and Laurent Ducasse1
Yoann Olivier2, Nicolas Martinelli2, Jérôme Cornil2, and David Beljonne2

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, B-7000 Mons, Belgium
Molecular dynamics simulations have been coupled to Valence Bond/Hartree Fock (VB/HF) quantum-chemical calculations to evaluate the impact of diagonal and off-diagonal disorder on charge carrier mobilities in self-assembled one-dimensional 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
Laboratoire de Chimie Théorique, UCPTS, Facultés Universitaires Notre-Dame de la Paix, Rue de Bruxelles, 61, B-5000 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 Huang-Te 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 second-order Møller-Plesset (MP2) perturbation theory and the coupled-cluster with single and double and perturbative triple excitations (CCSD(T)) theory. With increasing basis size, a large basis set (aug-cc-pVTZ) 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 4-site 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 atom-wise radial distribution functions and the self-diffusion coefficients over a wide range of experimental conditions.
Ultrafast electronic motion in hydrogen molecular ion induced by a high power intense laser
H. Mineo1 , Y. Teranishi2 , S.D. Chao1, and S.H. Lin3,4
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 23-166, Taipei 106, Taiwan ROC
4 Institute of Applied Chemistry, Institute of Molecular Science, Chiao-Tung University, Hsin-Chu, 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 Keldysh-Faisal-Reiss (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.
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 H2n+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 H5+ 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 first-principles electronic structure calculations within the DFT framework is adopted. Such DFT approach using the B3(H) hybrid functional, specially designed for hydrogen-only 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 H5+ 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 zero-point structure of H5+ cluster [3]. Such findings are of particular interest for studying larger species of the Hn+ clusters, as well as gas-phase solvation effects, cluster fragmentation, and collision processes in astrophysical applications[4,6].


[1] A. Aguado, P. Barragán, R. Prosmiti, G. Delgado-Barrio, P. Villarreal, and O.Roncero J. Chem. Phys. 133, 024306 (2010).
[2] P. Barragán, R. Prosmiti, O. Roncero, A. Aguado, P. Villarreal, and G. Delgado-Barrio, J. Chem. Phys. 133, 054303 (2010).
[3]R. Pérez de Tudela, P. Barragán, R. Prosmiti, P. Villarreal, and G. Delgado-Barrio, 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. Endo1, H. Shinomiya1, T. Ida2, S. Shimada2,K. Takahashi1, Y. Suzuki3, H. Yajima1
1Center for Colloid and Interface Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 Japan,
2Laboratory of Theoretical Chemistry, Graduate School of Natural Science and Technology, Kanazawa University, Kanazawa 920-1192, Japan,
3Advanced Development and Supporting Center, RIKEN, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan
Valence X-ray 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 found-out to be due to four component contributions of chitosan (Chito), diamond-like 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 MO-DFT 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.

[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. 37,21-29(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, 344-347(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 Endo1, Tomonori Ida2, Shingo Shimada2
1Research Center for Colloid and Interface Science, Tokyo University of Science 1-3, Kagurazaka, Shinjuku-ku 162-8601, Japan,
2Laboratory of Theoretical Chemistry, Graduate School of Natural Science and Technology, Kanazawa University, Kanazawa 920-1192, 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/6-31G** 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.

[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).
Laser-induced 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 laser-induced electronic and nuclear coherent motions of chiral molecules were presented. We have recently found by quantum dynamical simulations that transient unidirectional motions of &pi-electrons in an ansa (planar-chiral) 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 &pi-electrons. In this report, we clarify the nonadiabatic coupling effects on the coherent dynamics of chiral aromatic molecules.
Second Hyperpolarizabilities of Open-Shell Singlet Extended Metal Atom Chains (EMACs)
Hitoshi Fukui,1 Yudai Inoue,1 Yasuteru Shigeta,1 Benoît Champagne2 and Masayoshi Nakano1
1Graduate School of Engineering Science, Osaka University, Japan
2Laboratoire de Chimie Théorique, Facultés Universitaires Notre-Dame de la Paix (FUNDP), Belgium
We have theoretically investigated open-shell 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 closed-shell 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 d-orbitals [3]. In particular, open-shell singlet extended metal atom chains (S-EMACs), 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 d-orbitals, 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 S-EMACs 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 Kohn-Sham Local Density Approximation
Department of Advanced Reactor System Engineering
Toshiba Nuclear Engineering Service Corporation
8, Shinsugita-cho, Isogo-ku, Yokohama, 235-8523, 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 Kohn-Sham formalism, since the magnetic properties by GGA (generalized gradient approximation) are similar to the original Kohn-Sham results than those by the VWN (Vosko-Wilk-Nusair) 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 O2- 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 CaCuO2 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 O2- 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.

[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. Glushkov1,2
1 Odessa University, Odessa-9, 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 Gell-Mann 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 Kohn-Shan and Dirac equations states of the finite Fermi-systems 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, multi-photon 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 mean-field (plus Dirac-Woods-Saxon) model for the ground-state 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 NAS1-3, 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, 505-585 (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 NAS-4, Moscow-Troitsk (1991).
Laser Electron-Gamma-Nuclear Spectroscopy of Atoms and Multicharged Ions and NEET Effects in Heavy Nuclei: Relativistic Energy Approach
Alexander V. Glushkov,1,2 Olga Yu. Khetselius1 Svetlana Malinovskaya1 and Andrey A. Svinarenko1
1Odessa University, Odessa-9, SE, Ukraine

2ISAN, 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 electron-gamma-nuclear processes in atoms, ions, nuclei and resonant NEET (NEEC) processes in heavy nuclei, based on the relativistic density functional (DF) formalism and energy approach (S-matrix formalism of Gell-Mann and Low) [2]. Decay and excitation probability is linked with the imaginary part of energy of the excited state for the “electron shell- nucleus-photons” system. For radiate decays it is manifested as effect of retarding in interaction and self-action and calculated within QED- DFT theory [2]. We firstly present data about intensities of the electron satellites in gamma-spectra of nuclei in the neutral (low lying transitions) and multicharged O-and F-like 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.
[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 AS-4, 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 Large-Scale 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 light-triggered or light-powered 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 excited-state energy, property, and dynamics calculations for larger systems than previously possible, we have recently developed new implementations of the configuration interaction singles (CIS) and Tamm-Dancoff time-dependent density functional theory (TDA-TDDFT) approaches which utilize massively multi-parallel 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 Hartree-Fock and Kohn-Sham DFT GPU implementations [1-3], these programs utilize a direct algorithm, in which the one-electron matrix elements and two-electron 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 speed-ups 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 multiple-spawning 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 time-dependent electron-nuclear wavefunction
E.K.U. Gross
Max Planck Institute for Microstructure Physics, Weinberg 2, D-06120 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 photo-synthesis. Standard approximations such as Ehrenfest dynamics, surface hopping, or nuclear wave-packet dynamics only partially capture the non-adiabatic effects. As a first step towards a full ab-initio treatment of the coupled electron-nuclear system, we deduce an exact factorization of the complete wavefunction into a purely nuclear part and a many-electron 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 time-dependent potential energy surfaces as well as time-dependent 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 electron-ion dynamics. In particular, the time-dependent 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 Gu1,2
1Center for Computational Quantum Chemistry, South China Normal University, Guangzhou, Guangdong 510631, China;
2CREST, Japan Science and Technology Agency (JST), Kawaguchi, Saitama, Japan
The elongation method is presented for linear scaling Hartree-Fock 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 bio-and nano-systems, 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 time-dependent Hartree-Fock (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 bio-molecules, polymers, and nano-materials. It is expected to provide a tool for designing NLO materials and studying physical/chemical properties of huge systems.

[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 97-177, 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 Nyulászi3

1Eenheid Algemene Chemie (ALGC), Member of the QCMM Research Group – Alliance Ghent-Brussels, Vrije Universiteit Brussel (VUB), Pleinlaan 2, B-1050 Brussels, Belgium
2Department of Chemistry, University of Durham, South Road, Durham, DH1 3LE UK.
3Department 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, H-1111, Hungary
In the early 90's it has been shown that d-orbitals do not participate in the bonding of neutral molecules containing heavy atoms [1]. This founding is in agreement with the ionization energies of the pyridine-stibabenzene series obtained by photoelectron spectroscopy, where the A2 ionized states have almost constant energy within the series [2]. Since the a2 orbitals have two planar nodes through the heteroatom, they are relatively unperturbed by the heteroatom, and a d-orbital interaction would stabilize an A2 cationic state. In contrast to this, the electron transmission investigation of the electron affinities of the same series [3] revealed that A2 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 d-orbitals in the valence shell.
We have investigated the d-orbital contribution in the semi-occupied molecular orbitals of the pyridine-stibabenzene and furan-tellurophene series in both low-lying 2A2 and 2B1 anionic states by means of a newly developed, "potential wall confinement" technique [4]. We found a significantly increase in the heteroatom d-orbital contributions of the semi-occupied a2 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 B1 anionic states are the same, however, due to symmetry reasons the heteroatom perturbs the b1 orbitals more significantly than the a2 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)
Enzyme-inhibitor 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 enzyme-inhibitor interaction. The pairwise analyses between efavirenz and individual residue in the binding pocket of both WT and K103N HIV-1 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.

1. Srivab, P. and Hannongbua, S.*, A study of the binding energies of efavirenz to wild-type and K103N/Y181C HIV-1 reverse transcriptase based on the ONIOM method, Chem. Med. Chem., 3(5), 803-811 ( 2008)
2. Maitarad, P., Kamchonwongpaisan, S., Vanichtanankul, J., Vilaivan, T., Yuthavong, Y., Hannongbua, S.*, Interactions between Cycloguanil Derivatives and Wild-Type and Resistance-Associated Mutant P. falciparum Dihydrofolate Reductases, J.Comput-Aided Drug Des., 23(4), 241-252 ( 2009)
3. Sae-Tang, D., Kittakoop, P., and Hannongbua, S., Role of Key Residue Specific to Cyclooxygenase II : An ONIOM Study, Monatsh. Chemie, 140, 1533-1541 ( 2009).
4. Vailikhit, V, Holzschuh, W.J. and Hannongbua, S., 1H-NMR chemical shifts of some DMSO-solvated amines using MDONIOM2, J. Mol.Struct. ( THEOCHEM), 944, 173-176 ( 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 HIV-1 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 photo-functional proteins: SAC-CI study
Jun-ya Hasegawa
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University
In the vision and fluorescent proteins, controlling photo-absorption/emission energy of chromophore is the essential to furnish a protein with the photo-functionality. Retinal Schiff base in vision, luciferin in insects, and green-fluorescent 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 photo-absorption/emission energies.

The present talk summarizes some recent theoretical studies on the spectral tuning mechanism in photobiology using quantum chemical calculations with the symmetry-adapted cluster configuration interaction (SAC-CI) method. SAC-CI is a coupled-cluster 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 SAC-CI 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) 1140-1148. [2] N. Nakatani, J. Hasegawa, H. Nakatsuji, J. Am. Chem. Soc. 129 (2007) 8756-8765; N. Nakatani, J. Hasegawa, and H. Nakatsuji, Chem. Phys. Letters 469 (2009) 191-194. [3] J. Hasegawa, T. Ise, K. Fujimoto, A. Kikuchi, E. Fukumura, A. Miyawaki, and Y. Shiro, J. Phys. Chem. B, 114(8), 2971-2979 (2010).
Singlet Fission for Dye-Sensitized Solar Cells
Zdenek Havlas1, Josef Michl1,2
1Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nam. 2, 16610 Prague6, Czech Republic
2Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215, United States
Singlet Fission is a spin-allowed 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 spin-spin 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(S1) ≥ 2 E(T1) but also E(T2) ≥ 2 E(T1). We have observed that 1,3-diphenyl-isobenzofuran satisfies these conditions and yields 200% of triplet states in a crystalline state.
- For practical reasons, the S1 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 self-organization 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 TiO2 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 metal-atom 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 plasmon-related 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 metal-atom cluster systems. We take several chromophore molecules and simple metal-atom systems. For cluster systems, we further consider two particular structures: chain and ring in order to make clear definition of “plasmon-like” 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 Franck-Condon Factors?
Ray Hefferlin,1 Jonathan Sackett1 and Jeremy Tatum2
1Southern Adventist University, Collegedale, TN 37315, USA
2University 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 proton-shift away from "rare-gas" molecules, such as LiNe. Our preliminary results are shown here. The rare-gas molecules are indicated by vertical lines and by parentheses around their names.

Fig. 1. The 13-electron molecules are CN, BO, BeF, (LiNe), (NaHe), and MgH.The bands are A2Π+-X2Σ.

Fig. 2. The 22-electron molecules are Na2, (MgNe), AlF, SiO, PN, SC, BCl, and (BeAr). The bands are A1Π-X1Σ+.

Fig. 3. The 21-electron molecules are (NaNe), MgF, AlO, SiN, PC, BS, BeCl, (LiAr), (KHe), and CaH. The bands are B2Σ+-X2Σ+.
Theories and applications for electronic coupling in triplet energy transfer
Chao-Ping 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 opto-electronic devices. The electronic coupling factor is an off-diagonal 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 light-harvesting complexes will also be discussed. In particular, TET the bacterial light-harvesting complex II (LH2) of Rhodospirillum molischianum and Rhodopseudomonas acidophila, and the peridinin-chlorophyll a protein (PCP) from Amphidinium carterae. The TET rates were estimated based on the couplings obtained. For all light-harvesting 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 π-conjugation lengths in the carotenoids and their analogs reported in the literature. Our results provide theoretical limits to the possible photophysics in the light-harvesting complexes.

Linearity condition for orbital energies for hybrid functionals
Yutaka Imamura,1 Rie Kobayashi1 and Hiromi Nakai1,2
1Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, JAPAN

2Research Institute for Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, JAPAN
We propose the linearity condition for constructing an orbital-specific (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. Breedlove5
1Department of Advanced Materials Science, Faculty of Engineering, Kagawa University

2Department of Chemistry, Faculty of Science, University of Toyama

3Department of Chemistry, Faculty of Science, Okayama University of Science

4Division of Chemistry, Graduate School of Science, Hokkaido University

5Department 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 ([Cu2(μ-X)2L] (X = Br and I) (L = N-heteroaromatic 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 π-conjugated 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 ([Cu2(μ-X)2L] 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 transition-metal 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 oxidation-reduction 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 Born-Haber 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 = 1021 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 table-top 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 μ-oxo ligands are synthesized as model of the oxygen-evolving 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 exchange-correlation 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 manganese-μ-oxo systems. In addition, the most reliable functional for estimations of s-d 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 Kapralova-Zdanska1,2 and Jan Smydke1,2
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 electro-magnetic 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 time-dependent wavefunction, see below. Time-dependent 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 non-adiabatic processes for calculating the populations of states with a long life-time (whether they are low-lying continuum states, which are indeed rotated into the complex plane due to complex scaling, but their imaginary components are still small, or just the long-lived 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 time-dependent wave function is still advantageous as it ensures an effective separation of the fast time-dependence (due to field oscillation) and slow time-dependence (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
About 10 years ago it was found that neutron scattering on hydrogen showed anomalously low cross-sections 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 τsc = 10-16 – 10-15 s range). The anomalies decreased with the neutron energy, which meant that the cross-sections 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 cross-section are cancelled through the large zero-point 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.

Time-dependent multiconfiguration wave function theory for molecular systems composed of two kinds of Fermi particles: Application to diatomic-like 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 "diatomic-like molecular picture" for molecules such as CH3OH, C2H2, and CH2CH2.
  First, we calculate the electro-protonic ground state wave function of CH3OH 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 Born-Oppenheimer approach, which assures applicability of our present non-Born Oppenheimer approach.
  Another example includes the calculation of the CI-vectors that are newly introduced in our theory to elucidate the physical meaning of the CI-vectors. From the analysis of the electro-vibrational ground state wave function of 1D hydrogen molecule, we find that the effects of non-adiabatic couplings between adiabatic electronic states in the Born-Oppenheimer picture are properly described in the present method as the variations of the CI-vectors.
Ab initio and density functional calculation of calcium binding sphingomyelin lipid molecules: A pin holder model approach
Hiroyuki Kawabe1 and Kimikazu Sugimori2
1Department of Social Work, Faculty of Social Work, Kinjo University, Japan

2Department of Physical Therapy, Faculty of Health Sciences, Kinjo University, Japan
One of the phospholipids, sphingomyelin (SM, N-acyl-sphingosine-1-phosphorylcholine) 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 co-workers have shown that human lens sphingomyelin and its hydrogenated derivative, dihydrosphingomyelin (DHSM) are interacted with Ca2+ ions to develop human cataracts [1,2]. Previously we have investigated conformational differences between an isolated SM / DHSM molecule and Ca2+ -coordinated form by using density functional theory (DFT) which B3LYP functional and 6-31G(d,p) double-zeta split-valence 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, 31P-Nuclear Magnetic Resonance (NMR) shielding constants of the obtained conformers are investigated by using ab initio and DFT with gauge invariant atomic orbitals (NMR-GIAO) calculations [4].
In this study, we apply previous results to dimer and trimer model of lipid molecules with Ca2+ 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 Ca2+ are fully optimized. We analyze potential energy surface (PES) with the fixed parameters that are length between tails of lipid and coordinate of Ca2+ approaching from outer region to phosphate.

[1] M. Rujoi, D. Borchman, D. B. Dupré, and M. C. Yappert, Biophys. J. 82 (2002) 3096-3104.
[2] M. C. Yappert and D. Borchman, Chem. Phys. Lipids 129 (2004) 1-20.
[3] K. Sugimori, H. Kawabe, H. Nagao and K. Nishikawa, Int. J. Quantum Chem. 108, 2935-2942 (2008). doi:10.1002/qua.21858
[4] K. Sugimori, H. Kawabe, H. Nagao, and K. Nishikawa, Int. J. Quantum Chem., 109 (2009) 3685-3693. 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 920-1192 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,
Sakyo-ku, Kyoto 606-8501, Japan
*Debrecen University, H-4010 Debrecen, Hungary
Manne Siegbahn once wrote that “the curve (bremsstrahlung from X-ray tube) rises abruptly on the short wave-length 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 [2-4]. The Planck’s blackbody equation is expressed through the Tsallis nonextensive entropy [5]: N(E)=1/[(1+(q-1)x)1/(q-1)-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 long-range 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.

[1] M. Siegbahn, “The Spectroscopy of X-Rays”, 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, X-Ray 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 Zero-Field 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 co-workers 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 zero-field splitting parameters caused by mainly spin-orbit 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, single-molecular 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 coupled-perturbed equation. This method is involved in their program package "ORCA". Thus, we also evaluated ZFS parameters by Neese's methods.
Free energy of cell-penetrating peptide in lipid bilayer membrane: coarse-grained simulation
Shuhei Kawamoto1, Takeshi Miyakawa2, Masako Takasu2, Ryota Morikawa2, Tatsuki Oda1, Hiroaki Saito1, Shiroh Futaki3 and Hidemi Nagao1
1Graduate School of Natural Science and Technology, Kanazawa University
2School of Life Sciences, Tokyo University of Pharmacy and Life Sciences
3Institute for Chemical Research, Kyoto University
Cell-penetrating 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 all-atom 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 coarse-grained 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.
Nuclear-Relativistic Many-Body Perturbation Theory to Parity Nonconservation Effect in Heavy Atoms and Nuclei
Olga Yu. Khetselius
Department of Mathematics, Odessa OSENU University, Odessa-9, Ukraine
During the past two decades, the nuclear and atomic-optical experiments to detect parity non-conservation (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 6s2S1/2-5d2D3/2 transition of the Ba+. In our paper we systematically apply the nuclear-relativistic many-body 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 exchange-correlation, Breit, weak e-e interactions, QED and nuclear (magnetic moment distribution, finite size, neutron skin) corrections, nuclear-spin dependent corrections due to anapole moment, Z-boson [(AnVe) current] exchange, hyperfine-Z exchange [(VnAe) current]. The weak charge is found for 133Cs, 205Tl and 173Yb and comparison with Standard Model is done. Using the experimental value (EPNC/b)= 39mV/cm (Tsigutkin et al, 2009) and our calculated amplitude value 9.707*10-10 ieaBone could find for 173Yb (Z=70, N=103) the weak charge value QW=-92.31 (the SM gives QW=-95.44). The received data are compared with known earlier and recent results [1,2]. The role of the nuclear effects contribution (core-polarization contributions, which are induced by valent protons of a nucleus), spatial distribution of magnetization in a nucleus (the Bohr-Weisskopf effect), neutron skin correction and the non-accounted high order QED corrections are analyzed.
[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 Lacivita2, Roberto Dovesi2 and Heribert Reis3
1Department of Chemistry and Biochemistry, University of California, Santa Barbara, USA
2Departimento di Chimica IFM, Universitá di Torino, Italy
3The National Hellenic Resarch Foundation, Athens, Greece
About a dozen years ago it was observed that Kohn-Sham 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 exchange-correlation 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 inter-molecular distances. Although long-range corrected functionals may mitigate this effect to some extent, it is not clear that they systematically improve upon the Hartree-Fock 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 coronene-type 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 field-induced 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 Nakamura1 and Yu Takano1
1Institute 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/6-311++G(2d,2p)) with PCM (polarizable-continuum 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 gas-phase 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.

[1] Takano, Y.; Houk, N. K. J. Phys. Chem. A 2004, 108(52), 11740-11751.
[2] Ribeiro, J. M. A.; Ramos, J. M.; Fernandes, A. P. J. Chem. Theory Comput. 2010, 6(8), 2281-2292.
Two-layer 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 broken-symmetry (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 spin-projection method to eliminate the SCE from the energy derivatives based on Yamaguchi’s approximate spin projection (AP) procedure [1-4]. 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 single-point 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 low-spin and the high-spin 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 spin-restricted (R) methods, i.e. two-layer QM/QM’ approach based on ONIOM method. In the method, the effect of the outer-ligands 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.

[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 (SAC-CI) and the third order algebraic diagrammatic construction scheme [ADC(3)]
S. Knippenberg1 and B. Hajgató
1 Service de Chimie des Matériaux Nouveaux, Université de Mons, Place du Parc 20, B-7000 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 (SAC-CI) 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 photo-electron 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 outer-valence Green's function (OVGF) and SAC-CI/SD-R calculations. Since ADC(3) only includes 2h-1p shake-up states, while SAC-CI general-R also includes higher order ones, the agreement between both methods assures that the higher order shake-up states do not play an important role in the ionization spectra of norbornane. The band-12 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 nano-fiber including metal ions
Yu Komatsu,1 Shuhei Kawamoto,2 Takeshi Miyakawa,1 Ryota Morikawa,1 Masako Takasu,1 Satoshi Akanuma1 and Akihiko Yamagishi1
1School of Life Sciences, Tokyo University of Pharmacy and Life Sciences, Japan
2Graduate 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 nano-fiber 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 nano-fiber formation, we are testing three proteins: LARFH, Sulerythrin and IPMDH.
In this research, we analyzed the three proteins which are candidates for constructing a nano-fiber and investigated conditions that show high stability using molecular dynamics (MD). Sulerythrin contains two pairs of Zn2+ and Fe2+. 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 Gbind is calculated.

[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 V-Agdal
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 cyclo-adducts 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 .S2O 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 spin-orbit coupling is taken into account. One dimensional cuts of the three-dimensional potential energy surfaces are presented for linear and bent geometries. Anisotropy in regard of the different approaches is shown and the S-SO one seem to be favored.
A study of the sulfur chromophors are then presented and electronic excited states responsible of color of S3-, S4-, S4+ determined The PES and some spectroscopic constants of the lowest states of S3- are mapped using The SA-CASSCF and CCSD(T) accurate methods.


1) ‘Theoretical study of the mechanism of the 1,3-dipolar cycloaddition reaction of methyl-3-fluoro-3-trifluoromethyl prop-2-Enoate with Pyrroline-1-Oxyde’
K. Marakchi, H. Abou El Makarim, O. K. Kabbaj, N. Komiha
Phys. Chem. News 52 (2010) 128-136
2) ‘On the formation of S2O at low energies: An Ab-Initio study’
Isabelle Navizet, Najia Komiha , Roberto Linguerri, Gilberte Chambaud and Pavel Rosmus
Chemical Physics Letters, Volume 500, Issues 4-6, 19 November 2010, Pages 207-210
3) ‘Electronic states of the Ultramarine chromophore S3-‘

Control of Vibrational Dynamics and Reaction of C60 and Its Derivatives by Near-infrared Fields
Hirohiko Kono,1 Naoyuki Niitsu,1 Kaoru Yamazaki,1 Katsunori Nakai,2 Mikito Toda,3 and Stephan Irle4
1Department of Chemsitry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
2Department of Chemistry, School of Science, The University of Tokyo, Tokyo 113-0033, Japan.
3Department of Physics, Faculty of Science, Nara Women's University, Nara 630-8506, Japan.
4Department of Chemistry, Graduate School of Science, Nagoya University, Nagoya 464-8601, Japan
We developed the time-dependent (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 near-infrared (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 C60 interacting with intense IR pulses and found that large-amplitude vibration with energy of > 20 eV is induced mainly in the oblate-prolate hg(1) mode of C60 and its cations [2]. We also demonstrated that large-amplitude vibration of the hg(1) mode persists for 2-5 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 C60 on the ns time scale by using a DFTB method. It is confirmed that the main process is C2-elimination after Stone-Wales (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 field-induced 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 single-walled 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
E-mail: eugene.kryachko@ulg.ac.be
Generally speaking, an arbitrary 3D molecular structure is either space-filled, compact, without any void, or possesses some void(s) or emptiness that result in a hollow cage shape. Fullerenes, such as the buckyball C60, belong to the latter category. Similar fullerene-like 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 exo-reactivity, on the one hand, and the inner, void, or endo-reactivity 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, HOMO-LUMO 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 C60-fullerenes. A surprising confinement propensity of the 3D space-filled cluster Au20( Td) is under consideration as well.

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. Delgado-Barrio, 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 1-36, Nishikyo-ku, Kyoto 615-8245, Japan
  We derived necessary conditions for exact wave functions of the time-independent 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 inter-particle 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 HBr3+ and of double core holes
P Lablanquie
LCP-MR, CNRS and University Paris-VI
75231 Paris Cedex 05
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) HBr3+ 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 HBr3+ potential curves. They are purely dissociative to H+ + Br2+ limits, but present a peculiar topology due to the residual H + Br3+ binding, as confirmed in our ab initio calculations. [1]
-2) Double core holes have been produced by single photon double ionization. The two K-shell 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 bond-breaking 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 bond-breaking potential energy surfaces. The first approach is the coupled cluster singles, doubles with partial triples and quadruples based on the unrestricted Hartree-Fock (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 single-bond breaking processes than the UHF-based 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 bond-breaking 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 UHF-based CCSD(T).

[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 Non-adiabatic Processes by the Density Matrix Method
Y. L. Niu1 C. K. Lin1 C. Y. Zhu1 Y. Fujimura1 M. Hayashi2 and Sheng Hsien Lin1

1Department of Applied Chemistry, Institute of Molecular Science and Center for Interdisciplinary Molecular Science, National Chiao-Tung University, Hsinchu Taiwan
2Center for Condensed Matter Sciences, National Taiwan University, Taipei Taiwan
Using femto-second time-resolved experiments to study ultrafast processes, quantum beat is often observed. To analyze the fs time-resolved 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 non-adiabatic process. How to treat the effect of conical intersection on non-adiabatic processes and fs time-resolved spectra will be presented.
The Chemistry of Bioluminescence: An Analysis of Chemical Functionalities
Isabelle Navizet1, Ya-Jun Liu2, Nicolas Ferre3, Daniel Roca-Sanjuan4, Mickael Delcey4 and Roland Lindh4
1University of the Witwatersrand, South Africa
2Beijing Normal University, China
3Universités d'Aix-Marseille, France
4Uppsala 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 electron-donating fragment and how these are affected by the substrate-enzyme interaction. The understanding is based on details of how the peroxide -O-O- bond supports the production of electronically excited products and how the Charge Transfer Induced Luminescent, CTIL, mechanism, with the aid of an electron-donating group, lowers the activation barrier, to support a reaction in living organisms. For the substrate-enzyme complex it is demonstrated that the enzyme can affect the hydrogen-bonding around the CTIL controlling group resulting in a mechanism for color modulation. Finally, in the light of the purpose of the fragments of the luciferin-luciferase complex to provide key chemical functionalities we will analyse other luciferin-luciferase 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 Solid-State 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 non-bonded 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 long-range 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 fragment-based VCD calculations on molecular aggregates give a better agreement with experimental spectra than the Boltmann-weighted 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 large-sized chiral systems.
Exploring Multiple Potential Energy Surfaces
Satoshi Maeda,1,2 Koichi Ohno3 and Keiji Morokuma2,4
1The Hakubi Center, Kyoto University, Kyoto 606-8302, JAPAN
2Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, JAPAN
3Toyota Physical and Chemical Research Institute, Nagakute, Aichi 480-1192, JAPAN
4Department 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, ion-molecule reactions, spin-flip 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. Dõbé, S. Maeda, and K. Morokuma, ChemPhysChem 2010, 11, 3883.; H. Xiao, S. Maeda, and K. Morokuma, J. Phys. Chem. Lett. 2011, 2, 934.
Laser Electron-Gamma-Nuclear Spectroscopy of Diatomic and Multiatomic Molecules
Svetlana V. Malinovskaya,1 and Andrey A. Svinarenko2
1Department of Chemistry, Odessa University, Odessa-9, Ukraine

2Department of Mathematics, Odessa University, Odessa-9, Ukraine
An important class of problems connected with modelling the cooperative laser-electron-gamma-nuclear 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 gamma-nuclear and optical quantum transitions in molecules, intensities of the complicated gamma-transitions 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 electron-gamma-nuclear processes in different molecules [2] (including the set of electron or vibration-rotational satellites of the gamma-nuclear spectrum). The calculation results for the electron-gamma-nuclear transition probabilities in the diatomic (the nucleus 127I with E=203keV in molecule of H127I) and vibration-nuclear transition probabilities for some three-atomic XY2, five-atomic XY4 molecules are given. In particular, we present the results of calculation for the vibration-nuclear transition probabilities in a case of the emission and absorption spectrum of nucleus 188Os (E=155 keV) in the molecule of OsO4 and nucleus 191Ir (E=82 keV) in the molecule IrO4.
[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 AS-4, Moscow-Troitsk, (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 many-body systems. Application to liquid para-hydrogen.
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 many-body systems.
As in the Centroid Molecular Dynamics (CMD), in TGMD the N-body quantum system is mapped to an N-body classical system. The associated both effective Hamiltonian and effective force are computed within the Variational Gaussian Wave-packet (VGW) approximation. The TGMD is exact for the high-temperature 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 para-H2 molecules.
The Dirac equation: spin, Zitterbewegung, the Compton wavelength,
and the foundation of the electron mass
Jean Maruani
Laboratoire de Chimie Physique - Matière 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 half-integer 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 - Matière 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 N-particle 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 2-electron 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 Minaeva1 and Hans Agren2
1Department of Chemistry, Bogdan Khmelnitskij National University, Cherkasy, Ukraine
2Department 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 doubly-triplet excited singlet state. In order to lower the barrier one can add new non-paired electrons to the reacting system or induce spin flip for enhancement of the inter-system crossing to the singly-excited triplet state. This can be done by exchange interaction with paramagnetic transition metal, or by internal (spin-orbit coupling) and external magnetic fields. This is the key idea behind spin-catalysis [1-7].
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 singlet-triplet 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 O2 (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 O2 molecule has a triplet ground state and how it can react with stable organic substances at 36.7 C to produce water and CO2 if the processes are spin-forbidden? 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 O2 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 spin-forbidden and can be activated and controlled by oxidase enzymes. This should involve particular spin catalysis: the strictly controlled T-S transition in the enzyme active site with low activation energy, which does not produce any radicals, but only short-lived biradical intermediate. The T-S transition means the subsequent spin flip in the biradical.
We present DFT calculations of the electronic structure, zero-field 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, FADH2, nicotinamide, NAD+, NADH and active centers of glucose oxidase, copper amine oxidase, hemoglobin, horse-reddish 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 spin-selective photoprocesses in ZFS triplet states helps us to consider the influence of external magnetic field on the T-S 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) 998-1023.
2. B.F. Minaev, V.A. Minaeva. Spin-dependent binding of dioxygen to heme. Ukrainica Bioorganica Acta,2 (2008) 56-64.
3. B.F. Minaev. Solvent induced emission of singlet oxygen. J. Mol. Struct. (Theochem), 183 (1989) 207-214.
4. B.F. Minaev. Intensities of spin-forbidden transitions in molecular oxygen and selective heavy-atom effects. Int. J. Quant. Chem., 17 (1980) 367-374.
5. R. Prabhakar, P. Siegbahn, B.F. Minaev, H. Agren. Activation of dioxygen by glucose oxidase. J. Phys. Chem., B, 106 (2002) 3742-3750.
6. B.F. Minaev. Spin effects in reductive activation of O2 by oxidases. RIKEN Rev., 44 (2002) 147-149.
7. B.F. Minaev, H. Agren. Spin catalysis phenomena. Int. J. Quant. Chem., 57 (1996) 510-525.
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 560-8531, Japan
The intermonomer interaction effect on the electromagnetically induced transparency (EIT) for a dipole-coupled 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 near-degenerete 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, 6067-6076 (2010).
Variational path integral molecular dynamics method applied to molecular systems
Shinichi Miura
School of Mathematics and Physics, Kanazawa University, Kakuma, Kanazawa 920-1192, Japan
Variational path integral is a method to numerically generate the exact ground state of many-body systems [1]. Recently, the author has developed a molecular dynamics algorithm for the variational path integral calculation [2-5], which is called the variational path integral molecular dynamics (VPIMD) method. In my talk, some applications of VPIMD to molecular systems will be presented.

[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 Mg2+ in the H-ras GTP complex and in the H-ras GDP complex
Takeshi Miyakawa,1 Ryota Morikawa1, Masako Takasu1, Kimikazu Sugimori2, Kazutomo Kawaguchi3, Hiroaki Saito3 and Hidemi Nagao3
1School of Life Sciences, Tokyo University of Pharmacy and Life Sciences, Japan

2Department of Physical Therapy, Kinjo University, Japan

3Institute of Science and Engineering, Kanazawa University, Japan
In the H-ras GTP complex and the H-ras GDP complex, the coordination bonds between Mg2+ and oxygen atoms are very important. We derived the potentials of atoms around Mg2+ in H-ras GTP complex and in the H-ras 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 Mg2+, 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 Coherent-States and Density-Functional-Theory 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 [2-4]. END is a time-dependent, variational, non-adiabatic method for chemical dynamics that evaluates potential energy and interatomic forces “on the fly”, without employing predetermined potential energy surfaces. The simplest-level END (SLEND) [1] adopts a nuclear classical-mechanics description (as the zero-width limit of frozen Gaussian wave packets) and an electronic single-determinantal wavefunction. In the SLEND framework, three new developments will be presented:

1. The use of various types of coherent-states (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 valence-bond approach to a classical-electrostatics/charge-equilibration model based on the Sanderson principle of electronegativity equalization.

2. A new time-dependent Kohn-Sham density-functional-theory (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 Coherent-states Electron-nuclear dynamics) that utilizes several computer-science technologies [code parallelization, compute unified devise architecture (CUDA) devices, etc.]. The new developments are applied to the following chemical systems:

1. High-energy 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 proton-molecule reactions [7,8] with an emphasis on accurately predicting rovibrational, energy-transfer, and electron-transfer properties.

3. Various chemical reactions involving large reactants, such as Diels-Alder and SN2 reactions inter alia.

Results of the above simulations compare well with available experimental results.

[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 Single-Walled Carbon Nanotubes from Metal Clusters and SiO2 and SiC Surfaces: Density Functional Tight-Binding Molecular Dynamics Simulation
Stephan Irle,1 Alister J. Page,2 Biswajit Saha,2 Ying Wang,1 K. R. S. Chandrakumar,2 Yoshio Nishimoto,1 Hu-Jun Qian,1 and Keiji Morokuma2,3
1 Institute for Advanced Research and Department of Chemistry, Nagoya University, Nagoya 464-8602, Japan
2 Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, 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 on-the-fly 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 sp2 carbon phases, which begins with the formation of Y-junctions, 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.Saha1, T.K.Mukherjee1, P. K. Mukherjee2,3 and B. Fricke4
1Narula Institute of Technology, Agarpara, Kolkata 700109, India
2Department of Physics, Ramakrishna Mission Vivekananda University, Belur Math, Howrah, West Bengal 711202, India
3Department of Mathematics, Visva Bharati University, Santiniketan, West Bengal 731 235, India
4Institut 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. C4+, Al11+, Si12+, P13+, S14+, Cl15+ 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 1s2: 1Se--> 2s2:1Se; 2p2:1De, 2s2p:1Po, 2s3d:1De and 2p3d:1Fo. 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 Be2+ on the doubly excited 2pnp:1,3Pe and 2pnd:1,3De 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, H-4001 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 momentum-space 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 inner-shell ionization processes of atoms by charged-particle impact and study how the electron momentum distribution affects on the inner-shell ionization cross sections.

The momentum wave functions in various atomic models are calculated for arbitrary atomic orbitals. The nonrelativistic hydrogenic, the Hartree-Fock, the relativistic hydrogenic and the Dirac-Fock models are considered. The momentum wave functions are obtained as a Fourier transform of the wave functions in the position space. The Hartree-Fock and the Dirac-Fock wave functions in atoms are given in terms of Slater-type 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 inner-shell ionization cross sections by charged-particle impact in the binary-encounter approximation (BEA). The wave-function effect and the electronic relativistic effect on the inner-shell ionization processes are discussed.
Masataka Nagaoka1,2,†
1Graduate School of Information Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8601, JAPAN
2Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency (JST), Honmachi, Kawaguchi 332-0012, JAPAN
E-mail: mnagaoka@is.nagoya-u.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/MM-MD calculation [2], i.e., the ab initio QM/MM-FEG 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 (ZW-cis) to the neutral form (NF-cis) and other molecular structural changes among several NFs. Including the solvent effect explicitly by the ab initio QM/MM-FEG method, those stable-state 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 ZW-cis to NF-cis was found in very good agreement with not only the estimation by the Car-Parrinello MD method but also the previous experimental one. It is concluded that the ab initio QM/MM-FEG 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.Okuyama-Yoshida, M.Nagaoka, T.Yamabe, Int. J. Quantum Chem., Vol.70, 95 (1998); (b) N.Okuyama-Yoshida, 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,
H--4010 Debrecen
Ensemble non-interacting kinetic energy functional is constructed. The differential virial theorem is derived for the ensemble. A first-order differential equation for the functional derivative of the ensemble non-interacting kinetic energy functional is presented. A special case of the solution of this equation provides the original non-interacting kinetic energy of the density functional theory.
Relativistic Quantum Theory for Large Systems
Hiromi Nakai1 2 3
1Department of Chemistry and Biochemistry, Waseda University, Tokyo, Japan
2Research Institute for Science and Engineering, Waseda University, Tokyo, Japan
3CREST, Japan Science and Technology Agency, Tokyo, Japan
A number of relativistic quantum-chemical methods are available to treat compounds containing heavy elements. The four-component 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 two-component schemes. The infinite-order Douglas–Kroll (IODK) method [2-5] gives an exact description of the large component for the one-electron Dirac Hamiltonian. The IODK/IODK method [6], which transforms two-electron Coulomb operator by using the one-electron IODK unitary transformation, can reproduce the total energies for the four-component 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 two-component relativistic quantum-chemical 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.
Open-Shell 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 Ohta4
1Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
2Department of Chemistry, Graduate School of Science, Osaka University Toyonaka, Osaka 560-0043, Japan
3Laboratoire de Chimie Théorique (LCT), Facultés Universitaires Notre-Dame de la Paix (FUNDP) Rue de Bruxelles, 61, B-5000 Namur, Belgium
4Research Institute for Ubiquitous Energy Devices, National Institute of Advanced Industrial Science and Technology (AIST), Ikeda, Osaka 563-8577, Japan
Over two decades, the quest for efficient nonlinear optical (NLO) materials composed of molecular systems including organic π-conjugate molecules has been carried out both experimentally and theoretically. Most of the studies have been focused on the closed-shell systems, while there have been few studies on the open-shell systems. In the past years, we have proposed and analyzed a novel class of NLO systems, i.e., open-shell singlet systems, and have theoretically elucidated that these systems exhibit strong open-shell character and spin state dependences of the second hyperpolarizabilities (γ), and tend to show larger γ values in the intermediate open-shell character region than conventional closed-shell 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 open-shell molecular systems, including polyaromatic hydrocarbons and graphenes [3].

[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 Self-Consistent 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 Dirac-Coulomb equations with and without magnetic fields
Hiroyuki Nakashima and Hiroshi Nakatsuji
Quantum Chemistry Research Institute (QCRI) and JST-CREST, 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 Dirac-Coulomb 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 Dirac-Coulomb 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 multi-dimensional Dirac-Coulomb wave function (FC balance). The inverse Hamiltonian method and H-square quantity also with the complex scaling method [5] make numerically stable calculation possible even for the problematic Dirac-Coulomb 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.

[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 SAC-CI Method : Aperiodic System
H. Nakatsuji and T. Miyahara
Quantum Chemistry Research Institute and JST CREST
The SAC/SAC-CI method is a useful established coupled-cluster type method for studying ground, excited, ionized and electron attached states of molecules [1-3]. It is widely distributed through Gaussian09 [4]. Giant SAC-CI method [5] is designed to calculate giant-size molecular systems with the same accuracy as the ordinary SAC-CI method of small molecules. We want to realize seamless applicability of the SAC-CI method from small to large and even to giant-size molecular systems.
Previously, our applications of the giant SAC-CI 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 SAC-CI and very fine experiment may help to lead to a deeper understanding of the structure of proteins.

[1] Nakatsuji, H. Chem. Phys. Lett.1978, 59, 362.; 1979, 67,329,334; Bull. Chem. Soc. Jap. 2005, 78, 1705.
[2] SAC-CI 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 Takano2 and Ohgi Takahashi1
1Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, Japan
2Institute 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 water-soluble. 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 f-type polarization functions into basis sets improved the geometry optimizations using Hartree-Fock, MP2, and B3LYP, indicating that f-type polarization functions play an important role in the description of chemical bonds in sulfonamide derivatives.
Atomic Structure and Magnetic Anisotropy in the Small Iron-Platinum Clusters: from a First-Principles Study
Tatsuki Oda1, Shinya Haraguchi2, and Masahito Tsujikawa2
1Institute of Science and Engineering, Kanazawa University, Kanazawa 920-1192, Japan
2Graduate School of Natural Science and Technology, Kanazawa University, Kanazawa 920-1192, 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 OHNO1 and Yuto Osada2
1Toyota Physical & Chemical Research Institute, Japan

2Department 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 (l-ADDf), ratios of the computation time, the explored number of EQ and that of TS with respect to the full ADD following (f-ADDf) were systematically studied. When l-ADDf 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 f-ADDf. This tendency of l-ADDf 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 hetero-junction effect in polymer stabilized precious metal clsuters
Mitsutaka Okumura,1,2 Yasutaka Kitagawa,1 Takashi Kawakamai,1and Shushuke Yamanaka1
1Department of Chemistry, Graduate School of Science, Osaka University, Japan

2Core 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 low-temperature 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(N-Vinyl-2-pyrrolidone) [PVP; (C6H9ON)n] , abbreviated as Au:PVP, can oxidize p-hydroxybenzyl 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 (hetero-junction) 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 hetero-junctions, such as metal cluster-support junctions in heterogeneous catalysts, metal-ligands junctions in metal complex, active sites in enzymes, metal cluster-stabilizer 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 hetero-junction effect between Au clusters and PVP. The present theoretical study has been undertaken to explain the hetero-junction effect between PVP molecules and Au clusters as a first step for understanding the hetero-junction effect of the catalytic reactions over the polymer stabilized Au nanoclusters.
Origin of the variety of the Cu2S2 core structure of the CuA sites: a density functional theory study
Orio Okuyama1, Yasuteru Shigeta1,2, Haruki Nakamura1, and Yu Takano1

1Institute for Protein Research, Osaka University, Japan
2Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Japan
The CuA site, a proximate electron-transfer 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 (N2OR), the terminal acceptor in anaerobic respiration. The CuA 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 σu* ground state of the oxidized CuA 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 Cu2S2 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 σu* state of the Cu2S2 core rather than the πu state [1].
High resolution X-ray crystal structures of the CuA sites in several proteins have so far been reported. The three-dimensional structures of the Cu2S2 core of the CuA 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 Cu2S2 core structure of several CuA sites, we have examined electronic structures of the Cu2S2 core of the CuA 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 N2OR (PDB ID: 1FWX, 2IWF, 2IWK), and an engineered CuA azurin (PDB ID: 1CC3). DFT calculations were performed using the exchange-correlation functional, M06, because the M06 functional reproduces the energy difference of the Cu2S2 core between the σu* 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 6-311G++(df,pd) basis set.

[1] Y. Takano, Y. Shigeta, K. Koizumi, H. Nakamura, Int. J. Quantum Chem. in press.
Josep M. Oliva
Instituto de Quimica-Fisica "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 boron-based molecular higher architectural constructs.

[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. Viñas, F. Teixidor, J. Am. Chem. Soc. 127 (2005) 13538
[3] J.M. Oliva, D.J. Klein, P.v.R. Schleyer, L. Serrano-Andres, Pure Appl. Chem. 81 (2009) 719
[4] J.M. Oliva, L. Serrano-Andres, Z. Havlas, J. Michl, J. Mol. Struct: THEOCHEM 912 (2009) 13
[5] L. Serrano-Andrés, D.J. Klein, P.v.R. Schleyer, J.M. Oliva, J. Chem. Theory Comput. 4 (2008) 133
[6] L. Serrano-Andres, J. M. Oliva, Chem. Phys. Lett. 432 (2006) 235
Structure and dynamics of glutathione and glutathione-transferaseT2-2: 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 T2-2 in the presence and absence of glutathione in water solvent to analyze the dynamical structure of binding site of the ligand-protein 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 T2-2 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 36849-5312
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, one-electron concepts. Ionization operators in Fock space provide the connection between spectra and bonding concepts. Several accurate and computationally efficient self-energy 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 electron-correlation effects have shown the limits of one-electron 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 above-mentioned 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 non-polar molecules of halogens, chalcogens etc. were calculated: e.g., RIV(F+) = 0.255 Å, RIV(Br+) = 0.918 Å, RIV(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 R12 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: Î2 (O1.92+O1.92–), ÑÎ (C1.76+C1.76–), CO2 (C3.68+O1.84–), N2 (N2.69+N2.69–), NO (N1.87+O1.87–), NO2 (N3.83+O1.915–).
Considering the experimental R12 values there were also calculated the values of atomic charges in the ionized molecules, e.g. Î2+ (O2.87+O1.87–) and Î2 (O0.97+O1.97–). The radius of He+ ion was calculated. The possibility of estimation of ion co-ordination, 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.532-542.
2. Oshchapovskii V.V. Russian J. of Inorganic Chemistry, 2010, V.55, No. 3, p. 401-409.
3. Oshchapovskii V.V. Russian J. of Inorganic Chemistry (in press).

Computational study of structure, vibrational property and electrochemical reaction on a biased metal-water 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 high-efficiency 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 metal-water interface in an electrochemical environment [2-3]. 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 vacancy-manganese center in nanodiamond systems
Takao Otsuka,1 Yoshitaka Tateyama,2,3 Masahito Morita,4 Makoto Taiji1
1RIKEN Quantitative Biology Center (QBiC), Kobe, Hyogo, Japan
2International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), Tsukuba, Ibaraki, Japan
3CREST, Japan Science and Technology Agency (JST), Kawaguchi, Saitama, Japan
4WPI Immunology Frontier Research Center (iFReC), Osaka University, Suita, Osaka, Japan
We present our theoretical study on vacancy-manganese center in nanodiamond systems by electronic structure calculations. We investigate the stability of spin states in some vacancy-manganese complexes in nanodiamond by using cluster models calculations. From the analysis of electronic structures by density functional theory (DFT) and Hartree-Fock with the perturbative correction calculation (with unrestricted/restricted open-shell), we found that the high spin state of [V-Mn-V] 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 Dirac-Pauli 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 Active-Space Coupled-Cluster Methods
Piotr Piecuch,1 Jun Shen,1, Marta Włoch,2Jesse J. Lutz,1, Jeffrey R. Gour,3 and Wei Li4
1Department of Chemistry, Michigan State University, East Lansing, Michigan 48824, USA
2Department of Chemistry, Michigan Technological University, Houghton, Michigan 49931, USA
3Department of Chemistry, Stanford University, Stanford, California 94305, USA
4School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu 210093, China
The widely used coupled-cluster (CC) and equation-of-motion (EOM) CC methods, such as CCSD(T) and EOMCCSD, have difficulties with capturing stronger non-dynamic electron correlations characterizing chemical reaction pathways and excited states dominated by two-electron transitions that can often be addressed by exploiting the completely renormalized (CR) and active-space CC and EOMCC approaches. This talk will discuss recent advances in the development and applications of the CR and active-space CC/EOMCC methods, including the extension of the former approaches to larger reactive molecular systems via the local correlation cluster-in-molecule ansatz and its multi-level extension, and the exciting new possibility of merging the CR and active-space 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 CR-CC methods to non-traditional 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 I2s and I2p and electron affinities A2p for the second row open-shell atoms (Li to F) with the respective experimental data. This study was supported by the Russian Fund for Basic Research (grant 09-03-00113) 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.
Time-domain 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 state-of-the-art non-adiabatic molecular dynamics techniques, implemented within time-dependent 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 electron-phonon 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 quantum-dots: insights from time-domain ab initio studies”, Acc. Chem. Res., 42, 2005 (2009)
3. A. B. Madrid, H.-D. Kim, O. V. Prezhdo, “Phonon-induced dephasing of excitons in silicon quantum dots: multiple exciton generation, fission and luminescence”, ACS-Nano, 3, 2487 (2009)
4. C. M. Isborn, O. V. Prezhdo, “Quantum dot charging quenches multiple exciton generation: first-principles 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: time-domain density functional theory of charge carrier relaxation”, ACS-Nano, 3, 93 (2009).
6. S. A. Fischer, A. B. Madrid, C. M. Isborn, O. V. Prezhdo, “Multiple exciton generation in small Si clusters: A high-level, 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, 741-769.
[3] M. Quack, Mol. Phys. 1977, 34, 477-504.
[4] M. Quack, Chem. Phys. Lett. 1986, 132, 147-153.
[5] M. Quack, Chem. Phys. Lett. 1994, 231, 421-428.
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.


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).
Nino Russo
Dipartimento di Chimica and Centro di Calcolo ad Alte Prestazioni per Elaborazioni Parallele e Distribuite-Centro d’Eccellenza MURST, Università della Calabria, I-87030 Arcavacata di Rende, Italy. E-mail: 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 (Singlet-Triplet) and the electronic excitation energies (Q band of the UV-Vis spectra). In addition the way to compute the spin-orbit couplings that allow the possible intersystem crossing is presented and discussed [2].

Work performed with the financial support of Università della Calabria and MIUR (PRIN 2008F5A3AF_005).

[1] L. Petit, C. Adamo and N. Russo, J. Phys. Chem. B 109 (2005) 12214-12221.; L. Petit, A. D. Quartarolo, C. Adamo, N. Russo, J. Phys. Chem. B, 110 (2006) 2398-2404.; A. Quartarolo, N. Russo and E. Sicilia, Chem. Eur. J. 12 (2006) 6797-6803.; A. D. Quartarolo, N. Russo, E. Sicilia and F. Lelj, J. Chem. Theory Comput. 3 (2007) 860-869; Lanzo, I.; Russo, N.; Sicilia, E., J. Phys. Chem. B., 112 (2008) 4123-4130; 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) 1849-1857; 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) 912-920; S. G. Chiodo, N. Russo, J. Computat. Chem. 30 (2009) 832-839; S. Chiodo and N. Russo, Chem. Phys. Lett. 490 (2010) 90-96; A. D. Quartarolo, S. G. Chiodo, and N. Russo, J. Chem. Theory Comput., 6 (2010) 3176–3189.
Interactions with electromagnetic fields: The frequency-dependent magentizability
Marco Anelli, Dan Jonsson and Kenneth Ruud
Centre for Theoretical and Computational Chemistry
Department of Chemistry
University of Tromsø
N-9037 Tromsø
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 frequency-dependent 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 frequency-dependent magnetizability, is in contrast poorly understood. Indeed, even the definition of the frequency-dependent magnetizability appear unsatisfactory.
A theory for the frequency-dependent magnetizability has been presented by Raab and de Lange [1], and these authors have also considered the frequency-dependent permeability [2]. However, the expression derived for the frequency-dependent magnetizability is based on a number of assumptions, making the theory somewhat unsatisfactory.
In this talk, we will discuss our recent analysis of the frequency-dependent magnetizability, and propose a new way of deriving the frequency-dependent permittivity, inverse permeability and magnetizability starting from an analysis of the current-current 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 Oddershede1,2
1Department of Physics and Chemistry, University of Southern Denmark, Odense Denmark
2Quantum Theory Project, Department of Physics, University of Florida, Gainesville, Florida, USA
3Department 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 Saito1,3 and Wataru Shinoda2,3
1 Faculty of Mathematics and Physics, Institute of Science and Engineering, Kanazawa University, Kanazawa 920-1192 Japan
2 Nanosystem Research Institute (NRI), Research Institute of Advanced Industrial Science and Technology (AIST), Central 2, 1-1-1 Umezono, Tsukuba 305-8568, Japan
3 CREST, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, 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 (0-50 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, cross-sectional 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.
First-Principles 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 920-1192, 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 first-principles calculations on defects and impurities in the single-layer graphene and single-wall CNT. The spin-polalized density functional calculations are performed. In the case of adatom-vacancy pair, we find that its healing barrier to the perfevt material is in the range 0.06eV-0.5 eV. These results are consisten with an experimental value (0.3 eV) in the case of single-wall CNT.
Modifications for the electron and the polarization propagator formalisms
Masaaki Saitow1, Tomonori Ida2, and Yuji Mochizuki1
1 Department of Chemistry and Research Center for Smart Molecules, Rikkyo University, 3-34-1 Nishi-ikebukuro, Toshima-ku, Tokyo 171-8501, Japan
2 Department of Chemistry, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, 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 one-electron detachment process, a spin adapted formalism was derived by considering spin-coupling of the configuration space explicitly. And this approach gives improved description for the open-shell 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 Coulomb-Yukawa like electric field gradient potentials using their one-range addition theorems
Faculty of Science, Department of physics, Trakya university, Edirne, Turkey
Using one-range addition theorems established in Ref.[1] for Slater type orbitals and Coulomb-Yukawa like interaction potentials with the help of complete orthonormal sets of ψ^α-exponential 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 Non-Orthogonal Wave Functions: DFT Kohn-Sham Embedding Equations and Vacant States
Emma K. Shidlovskaya1,2
1Information Systems Management Institute, Riga, Latvia

2Institute 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 well-pronounced boundary effects [2].

To overcome limitations of the standard EMC model, we have treated cluster embedding problem in the frameworks of one-electron approximation with non-orthogonal wave functions. Equations for the cluster are obtained varying total energy of the system expressed in terms of non-orthogonal one-electron 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 Kohn-Sham one-electron equations is studied. We demonstrate that our variation procedure is compatible with Kohn-Sham method. Cluster embedding equations remain the same [3] if instead of Fock operator we use one-electron Kohn-Sham Hamiltonian.

For further applications of our cluster embedding method we should overcome limitations of one-electron 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 quantum-chemical 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. 11-18.
[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 [1-4]. 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.

[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. Delgado-Barrio, S. Wilson, Springer (2009).
Real-Time TDDFT Simulation for Coherent Phonon Generation
Yasushi Shinohara1, Kazuhiro Yabana1,2, Jun-Ichi Iwata2, Tomohito Otobe3 and George F. Bertsch4
1Graduate School for Pure and Applied Sciences, University of Tsukuba, Japan

2Center for Computational Sciences, University of Tsukuba, Japan

3Advanced Photon Research Center, Japan Atomic Energy Agency, Japan

4Department of Physics, University of Washington, USA
We have been developing a first-principles 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 time-dependent density-functional theory (TDDFT) solving the time-dependent Kohn-Sham equation in real-time, while the ion motion is described by classical mechanics with the force evaluated by the Ehrenfest theorem. We consider a dynamics under a spatially-uniform 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 (0-16 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 electron-hole excitations. In the DECP, the force is generated from real electron-hole 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).
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 independent-particle 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 isotope-induced additivity of chemical shift in benzene
Kimikazu Sugimori,1 Hiroyuki Kawabe2, and Hideto Shimahara3
1Department of Physical Therapy, Faculty of Health Sciences, Kinjo University, Japan

2Department of Social Work, Faculty of Social Work, Kinjo University, Japan

3Center 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 nuclear-electron interaction. Theoretical considerations and experimental alignments have been studied by ab initio molecular orbital (MO), density functional (DF) theory, and other empirical strategies. The Born-Oppenheimer (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 methan-like molecules and benzene derivatives. NMR shielding constants are calculated again on the average distance by using Gauge-Independent Atomic Orbital (GIAO) method with B3LYP/cc-pVTZ and CCSD/cc-pVTZ. The calculated isotope shifts will be discussed with relation to additivity, charge distribution, and experimental values.

[1] A. C. de Dios and C. J. Jameson. Annu. Rep. NMR Spectrosc. 29 (1994) 1-69.
[2] K. Sugimori and H. Kawabe, Int. J. Quantum Chem. 110 (2010) 2989-2995. doi: 10.1002/qua.22917
Computer-Modeling 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 metal-organic frameworks (MOFs), are three-dimensionally 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 nano-sized pores of 1-50 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 hydrogen-gas storage in fuel cell systems.

PCPs/MOFs are synthesized through self-assembly 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 host-guest systems. In our simulations, the host-guest interaction and topology of pores of model host compounds are systematically modulated. Through computer modeling, it will be shown that many-body (multi-site) 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 First-Principles Maxwell+TDDFT Multi-Scale Simulator for
Propagation of High-Intensity Laser Pulse
Takeru Sugiyama1,Yasushi Shinohara1,Tomohito Otobe2,Kazuhiro Yabana1,3 and George F. Bertsch4
1Graduate School for Pure and Applied Sciences, University of Tsukuba, Japan
2Center for Computational Sciences, University of Tsukuba, Japan
3Advanced Photon Research Center, Japan Atomic Energy Agency, Japan
4Department 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 light-wave, 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 spatially-uniform time-varying electric field solving the time-dependent Kohn-Sham equation in real-time [1,2]. We now extend it to a first-principles simulator calculating simultaneously the coupled nonlinear dynamics of electrons and electromagnetic field. Since the length-scale 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 Kohn-Sham 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=5×1012W/cm2 and ℏw=1.55eV (below calculated band-gap, 2.4eV), respectively. The upper panels show propagation of electromagnetic field. The lower panels show the ground-state 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 Born-Oppenheimer approximations
Brian T Sutcliffe
Service de Chimie quantique et Photophysique,
Univ. Libre be Bruxelles,
1050 Bruxelles, Belgium.
The Born and Born-Oppenheimer 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 Born-Oppenheimer 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
Yokohama-City University
Recently, we have developed some first-principles approaches for multi-component systems including both electrons and nuclei (or positron) quantum-mechanically: (I) Multi-component 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 6-31++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 H3O2- [5,6] and the mechanism of double proton transfer in porphycene molecule [8].

[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, 2701-2705 (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 so-called emeraldine salt (ES) – the doped semioxidized form of PANI. Experimental data [1, 2] indicate that ES can exist both in spin-silent and in spin-active 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 HCl-protonated 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 size-independent. 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 [4Fe-4S] cluster, [Fe4S4(SCH3)3(CH3COO)], in dark-operative protochlorophyllide oxidoreductase
Yu Takano,1 Yasushige Yonezawa,1 Yuichi Fujita,2 Genji Kurisu,1 and Haruki Nakamura1
1Institute for Protein Research, Osaka University, Japan

2Graduate School of Bioagricultural Sciences, Nagoya University, Japan
The [4Fe-4S] clusters play important roles in electron transfer and catalysis in ferredoxins and nitrogenases. Recently, a X-ray structure of the dark-operative protochlorophyllide oxidoreductase (DPOR) has been determined at 2.3 Å resolution [1]. The [4Fe-4S] 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 [4Fe-4S] clusters coordinated with four Cys residues. To examine the effect of the Asp ligation on the enzymatic activities, three NB-protein mutants, D36C, D36S, and D36A, were prepared. Although the D36C and D36S substitutions almost nullified the activity, the D36A mutant exhibited 13 % of the wild-type 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 non-protein 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 electron-donating 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, first-principles 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 Co-doped TiO2/VO2 diluted magnetic semiconductor multilayers, in which the reversibly tunable IEC is achievable via metal-insulator 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 state-of-the-art 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.
Ab-initio 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 well-controlled structures and enable the measurement of various magnetic properties in atomic resolution. Ab-initio calculations on magnetic nano-structures 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 one-particle problem is solved by means of the fully relativistic version of the Korringa-Kohn-Rostoker method using the multiple scattering formalism1. For thin magnetic films surface Green's function technique has been applied to treat the semi infinite substrate and embedded-cluster Green's function method2 is used for the proper description of deposited magnetic clusters. In order to find the magnetic ground-state of nano-clusters 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 Dzyaloshinsky-Moriya 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 on-site anisotropy. In the framework of the multiple scattering theory the exchange interactions can easily be calculated by the torque method proposed by Liechtenstein3. With the relativistic version of the torque method4 we are able to determine the full coupling tensor. By means of Monte Carlo simulations and atomistic spin dynamics complicated spin-spiral ground state configuration which has been detected experimentally by spin polarized STM measurements5
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. Melichercik1, L. F. Pasteka1, P. Neogrady1 and M. Urban1,2
1Comenius University, Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences,
Mlynska dolina, 842 15 Bratislava, Slovakia.

2Slovak 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 low-energy 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 [1-4]. 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•(H2O)n (n=1-3). 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 DFT-B3LYP and UMP2 calculations of microhydrated uracil•(H2O)n (n=1-5) complexes treated at the same time by a polarized continuum model (PCM) [6]. Due to the microsolvation AEAs and VDEs increase by 600-660 meV, and by more than 1100 meV, respectively, for U(H2O)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(H2O)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 DFT-B3LYP 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. LPP-0155-09) and VEGA-1/0520/10.

[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)
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 Franck-Condon 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 Bogoliubov-Tyablikov 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 non-perturbative 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 angular-momentum 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 anisotropy-transforming coefficients KqKii 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 ( Ki), and on component qi of the ranks K and Ki projected onto the recoil direction k. An important new conservation rule is revealed through the analysis, namely that the component qi is preserved in any scattering, or photolysis reaction. The coefficients KqKii 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 anisotropy-transforming coefficients beyond the axial recoil limit contain scattering S-matrix 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 non-conservation; (b) quasiclassical approximation of the molecular scattering function in the high- J limit. The talk also reviews recent experimental results on the photo-dissociation of a number of polyatomic molecules, and shows how the investigation of the values determined for the speed-dependent parameter â and higher-rank anisotropy parameters supported the interpretation of the photo-dissociation dynamics.
[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. Orr-Ewing, 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. Balint-Kurti 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 many-body Hamiltonian eigenvalue problem [1]. As was shown in the seminal work by Aspuru-Guzik 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 read-out part of the quantum register and the whole algorithm proceeds in an iterative manner.

We have tested its performance and applicability for non-relativistic as well as relativistic CI energy calculations. Non-relativistic QFCI calculations of the four lowest lying electronic states of methylene molecule (CH2), 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 Kramers-restricted CI calculations employing the QFCI algorithm have been applied to the spin-orbit coupling in the SbH molecule [4]. We have also designed the quantum circuits for the simplest proof-of-principle physical realizations of relativistic quantum chemical computations on quantum computers.

[1] Abrams, D. S.; Lloyd, S. Phys.Rev.Lett. 1999, 83, 5162–5165.
[2] Aspuru-Guzik, A.; Dutoi, A. D.; Love, P. J.; Head-Gordon, 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 H2O (left) and in D2O (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), pp5999-6010.
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 2-Component (X2C) relativistic methods[1], all-electron treatments that include both scalar relativistic effects and spin-orbit coupling effects from the outset have become much more practical, leaving the electron-correlation stage of the calculation as the rate determining step.
By treating some recent applications[2] of relativistic coupled-cluster 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 Density-Functional 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 Levy-Lieb 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 Levy-Lieb 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 semi-empirical 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 transition-metal 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 second-order nonilinear optical properties of coordination transition-metal containing compounds within time-dependent density functional theory. The study revealed that the metal-metal interactions existing in the coordinated polynuclear compounds make significant contributions to the second-order responses. The charge transfer process originated from the d1-d2 transitions has been identified to be one of the effective mechanisms for the second-order response in these kind of compounds. The study indicates that inorganic polynuclear transition-metal clusters could be the promising mid-to-far nonlinear optical materials and molecular devices due to the distinctive metal-to-metal charge-transfer character, optical transparency in IR region, diverse structural configurations and flexible coordinated organic/inorganic ligands. A series of potential IR-active second-order nonlinear optical transition-metal containing cluster compoumds are reproted. The study may benefit to the efforts that we have made in searching novel mid-to-far 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 Yamaguchi4

1Graduate School of Science, Osaka University, Japan
2Institute for Molecular Science, Japan
3Protein Institute, Osaka University, Japan
4TOYOTA 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 X-ray structure [2] and the optimized ones starting from the X-ray 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 in-and-around 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 X-ray 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 triple-zeta 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 exchange-correlation functionals, BHandHLYP, CAM-B3LYP, TPSSh, PBE0, PBEh35, HSEh1PBE, HSE1PBE, HSE2PBE, LC-wPBE, M06, M06-2X, M06-HF, 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.

[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, J-R. 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.
30-2, Shimomaruko 3-chome, Ohta-ku, Tokyo 146-8501, 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 Hartree-Fock-Roothaan 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.

[1] J.Yasui, to be published in Progress in Theoretical Chemistry and Physics as a selected paper in Internatinal Conference on DV-Xα Method Aug. 2010 in Kerea, Springer this summer.
Antidot Structure Dependences of Open-shell Characters and Aromaticities for Hexagonal Graphene Nanoflakes
Kyohei Yoneda,1 Yudai Inoue,1 Tomoya Inui,1 Yasuteru Shigeta,1 Takashi Kubo,2 Benoît Champagne3 and Masayoshi Nakano1
1Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Japan
2Department of Chemistry, Graduate School of Science, Osaka University, Japan
3Laboratoire de Chimie Théorique (LCT), Facultés Universitaires Notre-Dame de la Paix (FUNDP), BELGIUM
The open-shell singlet state of graphene nanoflakes is at the origin of their unique physico-chemical properties. In this study, we theoretically investigate the open-shell characters and aromaticities of hexagonal graphene nanoflakes with different sizes of antidot structures, using the long-range corrected spin-unrestricted density functional theory, LC-UBLYP, method. It is found that the open-shell character exhibits an oscillatory behavior with increasing the size of the antidot structure, and the nucleus-independent chemical shift (NICS) – an index of aromaticity – also depends on the open-shell 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 structure-property relationships in polymorphic systems
Koretaka Yuge
Department of Materials Science and Engineering, Kyoto University, Kyoto 606-8501, Japan
While structure-property 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 ab-initio 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 2-dimensional system to search ground-state structure in polymorphs.

[1] K. Yuge, J. Phys.: Condens. Matter 22, 125402 (2010).
Use of one-range addition theorems in evaluation of multicenter electric field integrals of Slater type orbitals and Yukawa-like 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 Yukawa-like interaction potential using their one-range addition theorems established in Ref.[1] with the help of complete orthonormal sets of ψα- 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
Mn-doped Thiolated Au25 Nanoclusters: Atomic Confguration, Magnetic Properties, and A Possible High-performance Spin Filter
M. Zhou,1 Y. Q. Cai,1 M. G. Zeng,1 C. Zhang,1,2 and Y. P. Feng1
1Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore, 117542
2Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543
We report an ab inito investigation on the ground-state atomic configuration, electronic structures, magnetic and spin-dependent transport properties of Mn-doped Au25 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 high-performance 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

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