XVIth International Workshop on
Quantum Systems in
Chemistry and Physics
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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).


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