Origin of the Enhancement of the Second Hyperpolarizabilities of Metal-Carbon Bonds

Shota Takamuku; Yasutaka Kitagawa; Takanori Nagami; Jun Ya Fujiyoshi; Benoît Champagne; Masayoshi Nakano

doi:10.1021/acs.jpca.6b05711

Origin of the Enhancement of the Second Hyperpolarizabilities of Metal-Carbon Bonds

Shota Takamuku, Yasutaka Kitagawa, Takanori Nagami, Jun Ya Fujiyoshi, Benoît Champagne, Masayoshi Nakano

Unite de recherche en chimie physique, theorique et structurale

Résultats de recherche: Contribution à un journal/une revue › Article › Revue par des pairs

Résumé

The spin-unrestricted coupled-cluster method was employed to investigate the origin of the second hyperpolarizabilities (I³) in model systems involving metal-carbon bonds with various bond lengths as a function of their diradical character (y) and charge transfer (CT). These systems exhibit unique features: (i) σ electrons give the dominant contribution to I³, (ii) the Ï€ electrons contribution to I³ is negative, (iii) when the bond length increases, I³ exhibits two positive extrema, which are associated with the CT nature and the intermediate diradical character, respectively, (iv) and one negative extremum corresponding to intermediate CT and diradical character, and (v) in the bond stretching process, the maximum I³ amplitude per σ bond is about 7 times larger than that per Ï€ bond. These features are significantly different from those observed in pure organic systems.

langue originale	Anglais
Pages (de - à)	6838-6848
Nombre de pages	11
journal	The Journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory
Volume	120
Numéro de publication	34
Les DOIs	https://doi.org/10.1021/acs.jpca.6b05711
Etat de la publication	Publié - 1 sept. 2016

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10.1021/acs.jpca.6b05711

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Quantum chemical design of open-shell nonlinear optical materials
CHAMPAGNE, B. (Responsable du Projet), SEIDLER, T. (Responsable du Projet), DE WERGIFOSSE, M. (Responsable du Projet) & Nakano, M. (Responsable du Projet)
1/04/14 → 31/12/21
Projet: Recherche
Subvention - Professeur de recherche Francqui
Nakano, M. (Rôle de support) & Castet, F. (Rôle de support)
1/09/12 → 31/12/15
Projet: Recherche
PAI n°P7/05 - FS2: Systèmes supramoléculaires fonctionnels (PAI P7/05)
CHAMPAGNE, B. (Co-investigateur), De Vos, D. (Responsable du Projet), Van der Auweraer, M. (Co-investigateur), Jérôme, C. (Co-investigateur), Lazzaroni, R. (Co-investigateur), Marin, G. (Co-investigateur), Jonas, A. (Co-investigateur), Du Prez, F. (Co-investigateur), Vanderzande, D. (Co-investigateur), Van Tendeloo, G. (Co-investigateur), Van Speybroeck, V. (Co-investigateur), NENON, S. (Chercheur) & STAELENS, N. (Chercheur)
1/04/12 → 30/09/17
Projet: Recherche

Contient cette citation

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title = "Origin of the Enhancement of the Second Hyperpolarizabilities of Metal-Carbon Bonds",

abstract = "The spin-unrestricted coupled-cluster method was employed to investigate the origin of the second hyperpolarizabilities (I3) in model systems involving metal-carbon bonds with various bond lengths as a function of their diradical character (y) and charge transfer (CT). These systems exhibit unique features: (i) σ electrons give the dominant contribution to I3, (ii) the {\"I}€ electrons contribution to I3 is negative, (iii) when the bond length increases, I3 exhibits two positive extrema, which are associated with the CT nature and the intermediate diradical character, respectively, (iv) and one negative extremum corresponding to intermediate CT and diradical character, and (v) in the bond stretching process, the maximum I3 amplitude per σ bond is about 7 times larger than that per {\"I}€ bond. These features are significantly different from those observed in pure organic systems.",

author = "Shota Takamuku and Yasutaka Kitagawa and Takanori Nagami and Fujiyoshi, {Jun Ya} and Beno{\^i}t Champagne and Masayoshi Nakano",

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doi = "10.1021/acs.jpca.6b05711",

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Origin of the Enhancement of the Second Hyperpolarizabilities of Metal-Carbon Bonds. / Takamuku, Shota; Kitagawa, Yasutaka; Nagami, Takanori et al.
Dans: The Journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol 120, Numéro 34, 01.09.2016, p. 6838-6848.

Résultats de recherche: Contribution à un journal/une revue › Article › Revue par des pairs

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T1 - Origin of the Enhancement of the Second Hyperpolarizabilities of Metal-Carbon Bonds

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AU - Kitagawa, Yasutaka

AU - Nagami, Takanori

AU - Fujiyoshi, Jun Ya

AU - Champagne, Benoît

AU - Nakano, Masayoshi

PY - 2016/9/1

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Origin of the Enhancement of the Second Hyperpolarizabilities of Metal-Carbon Bonds

Résumé

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Autres fichiers et liens

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Projets

Quantum chemical design of open-shell nonlinear optical materials

Subvention - Professeur de recherche Francqui

PAI n°P7/05 - FS2: Systèmes supramoléculaires fonctionnels (PAI P7/05)

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