Enhancement of the third-order nonlinear optical properties in open-shell singlet transition-metal dinuclear systems: Effects of the group, of the period, and of the charge of the metal atom

H. Fukui, Y. Inoue, T. Yamada, S. Ito, Y. Shigeta, R. Kishi, M. Nakano, B. Champagne

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

Metal-metal multiply bonded complexes in their singlet state have been predicted to form a novel class of "σ-dominant" third-order nonlinear optical compounds based on the results of dichromium(II) and dimolybdenum(II) systems (H. Fukui et al. J. Phys. Chem. Lett.2011, 2, 2063) whose second hyperpolarizabilities (γ) are enhanced by the contribution of the dσ electrons with an intermediate diradical character. In this study, using the spin-unrestricted coupled-cluster method with singles and doubles as well as with perturbative triples, we investigate the dependences of γ on the group and on the period of the transition metals as well as on their atomic charges in several open-shell singlet dimetallic systems. A significant enhancement of γ is observed in those dimetallic systems composed of (i) transition metals with a small group number, (ii) transition metals with a large periodic number, and (iii) transition metals with a small positive charge. From the decomposition of the γ values into the contributions of dσ, dπ, and dδ electrons, the γ enhancements are shown to originate from the dσ contribution, because it corresponds to the intermediate diradical character region. Furthermore, the amplitude of dσ contribution turns out to be related to the size of the dz atomic orbital of the transition metal, which accounts for the dependence of γ on the group, on the period, and on the charge of the metal atoms. These dependences provide a guideline for an effective molecular design of highly efficient third-order nonlinear optical (NLO) systems based on the metal-metal bonded systems.
langue originaleAnglais
Pages (de - à)5501-5509
Nombre de pages9
journalJournal of physical chemistry A
Volume116
Numéro de publication22
Les DOIs
étatPublié - 7 juin 2012

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Transition metals
Optical properties
Metals
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Decomposition
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title = "Enhancement of the third-order nonlinear optical properties in open-shell singlet transition-metal dinuclear systems: Effects of the group, of the period, and of the charge of the metal atom",
abstract = "Metal-metal multiply bonded complexes in their singlet state have been predicted to form a novel class of {"}σ-dominant{"} third-order nonlinear optical compounds based on the results of dichromium(II) and dimolybdenum(II) systems (H. Fukui et al. J. Phys. Chem. Lett.2011, 2, 2063) whose second hyperpolarizabilities (γ) are enhanced by the contribution of the dσ electrons with an intermediate diradical character. In this study, using the spin-unrestricted coupled-cluster method with singles and doubles as well as with perturbative triples, we investigate the dependences of γ on the group and on the period of the transition metals as well as on their atomic charges in several open-shell singlet dimetallic systems. A significant enhancement of γ is observed in those dimetallic systems composed of (i) transition metals with a small group number, (ii) transition metals with a large periodic number, and (iii) transition metals with a small positive charge. From the decomposition of the γ values into the contributions of dσ, dπ, and dδ electrons, the γ enhancements are shown to originate from the dσ contribution, because it corresponds to the intermediate diradical character region. Furthermore, the amplitude of dσ contribution turns out to be related to the size of the dz atomic orbital of the transition metal, which accounts for the dependence of γ on the group, on the period, and on the charge of the metal atoms. These dependences provide a guideline for an effective molecular design of highly efficient third-order nonlinear optical (NLO) systems based on the metal-metal bonded systems.",
author = "H. Fukui and Y. Inoue and T. Yamada and S. Ito and Y. Shigeta and R. Kishi and M. Nakano and B. Champagne",
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Enhancement of the third-order nonlinear optical properties in open-shell singlet transition-metal dinuclear systems : Effects of the group, of the period, and of the charge of the metal atom. / Fukui, H.; Inoue, Y.; Yamada, T.; Ito, S.; Shigeta, Y.; Kishi, R.; Nakano, M.; Champagne, B.

Dans: Journal of physical chemistry A, Vol 116, Numéro 22, 07.06.2012, p. 5501-5509.

Résultats de recherche: Contribution à un journal/une revueArticle

TY - JOUR

T1 - Enhancement of the third-order nonlinear optical properties in open-shell singlet transition-metal dinuclear systems

T2 - Effects of the group, of the period, and of the charge of the metal atom

AU - Fukui, H.

AU - Inoue, Y.

AU - Yamada, T.

AU - Ito, S.

AU - Shigeta, Y.

AU - Kishi, R.

AU - Nakano, M.

AU - Champagne, B.

PY - 2012/6/7

Y1 - 2012/6/7

N2 - Metal-metal multiply bonded complexes in their singlet state have been predicted to form a novel class of "σ-dominant" third-order nonlinear optical compounds based on the results of dichromium(II) and dimolybdenum(II) systems (H. Fukui et al. J. Phys. Chem. Lett.2011, 2, 2063) whose second hyperpolarizabilities (γ) are enhanced by the contribution of the dσ electrons with an intermediate diradical character. In this study, using the spin-unrestricted coupled-cluster method with singles and doubles as well as with perturbative triples, we investigate the dependences of γ on the group and on the period of the transition metals as well as on their atomic charges in several open-shell singlet dimetallic systems. A significant enhancement of γ is observed in those dimetallic systems composed of (i) transition metals with a small group number, (ii) transition metals with a large periodic number, and (iii) transition metals with a small positive charge. From the decomposition of the γ values into the contributions of dσ, dπ, and dδ electrons, the γ enhancements are shown to originate from the dσ contribution, because it corresponds to the intermediate diradical character region. Furthermore, the amplitude of dσ contribution turns out to be related to the size of the dz atomic orbital of the transition metal, which accounts for the dependence of γ on the group, on the period, and on the charge of the metal atoms. These dependences provide a guideline for an effective molecular design of highly efficient third-order nonlinear optical (NLO) systems based on the metal-metal bonded systems.

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