Third-order nonlinear optical properties of open-shell systems: Diradical character and spin state dependences

M. Nakano, H. Fukui, H. Nagai, T. Minami, R. Kishi, H. Takahashi, T. Kubo, K. Kamada, K. Ohta, B. Champagne, E. Botek

Research output: Contribution to journalArticle

Abstract

The third-order nonlinear optical (NLO) properties of open-shell singlet molecular systems are investigated using model and real molecular systems by the ab initio molecular orbital (MO) and density functional theory (DFT) approaches. The diradical character dependence of the second hyperpolarizability (γ) - the microscopic origin of the third-order NLO properties - is elucidated as well as its spin state dependence: γ values for the singlet systems with intermediate diradical character are remarkably enhanced as compared to those of closed-shell and pure diradical systems, and the γ values for intermediate diradical systems are significantly reduced by changing from singlet to triplet state. Such features are exemplified by two-site diradical model systems, diphenalenyl diradicaloids, and nanographenes. The γ values of multi-radical systems including one-dimensional diphenalenyl diradical clusters are also examined, while the intermolecular interaction effects and the size dependence of γ per unit are discussed toward realizing a new class of open-shell NLO materials.
Original languageEnglish
Pages (from-to)43-53
Number of pages11
JournalAIP Conference Proceedings
Volume1108
DOIs
Publication statusPublished - 1 Jan 2009

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optical properties
optical materials
atomic energy levels
molecular orbitals
density functional theory
interactions

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Nakano, M. ; Fukui, H. ; Nagai, H. ; Minami, T. ; Kishi, R. ; Takahashi, H. ; Kubo, T. ; Kamada, K. ; Ohta, K. ; Champagne, B. ; Botek, E. / Third-order nonlinear optical properties of open-shell systems : Diradical character and spin state dependences. In: AIP Conference Proceedings. 2009 ; Vol. 1108. pp. 43-53.
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Third-order nonlinear optical properties of open-shell systems : Diradical character and spin state dependences. / Nakano, M.; Fukui, H.; Nagai, H.; Minami, T.; Kishi, R.; Takahashi, H.; Kubo, T.; Kamada, K.; Ohta, K.; Champagne, B.; Botek, E.

In: AIP Conference Proceedings, Vol. 1108, 01.01.2009, p. 43-53.

Research output: Contribution to journalArticle

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T1 - Third-order nonlinear optical properties of open-shell systems

T2 - Diradical character and spin state dependences

AU - Nakano, M.

AU - Fukui, H.

AU - Nagai, H.

AU - Minami, T.

AU - Kishi, R.

AU - Takahashi, H.

AU - Kubo, T.

AU - Kamada, K.

AU - Ohta, K.

AU - Champagne, B.

AU - Botek, E.

PY - 2009/1/1

Y1 - 2009/1/1

N2 - The third-order nonlinear optical (NLO) properties of open-shell singlet molecular systems are investigated using model and real molecular systems by the ab initio molecular orbital (MO) and density functional theory (DFT) approaches. The diradical character dependence of the second hyperpolarizability (γ) - the microscopic origin of the third-order NLO properties - is elucidated as well as its spin state dependence: γ values for the singlet systems with intermediate diradical character are remarkably enhanced as compared to those of closed-shell and pure diradical systems, and the γ values for intermediate diradical systems are significantly reduced by changing from singlet to triplet state. Such features are exemplified by two-site diradical model systems, diphenalenyl diradicaloids, and nanographenes. The γ values of multi-radical systems including one-dimensional diphenalenyl diradical clusters are also examined, while the intermolecular interaction effects and the size dependence of γ per unit are discussed toward realizing a new class of open-shell NLO materials.

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