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

Résultats de recherche: Contribution à un journal/une revueArticle

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 originaleAnglais
Pages (de - à)6838-6848
Nombre de pages11
journalJournal of physical chemistry A
Volume120
Numéro de publication34
Les DOIs
étatPublié - 1 sept. 2016

Empreinte digitale

Charge transfer
Carbon
Metals
charge transfer
Bond length
range (extremes)
augmentation
carbon
metals
Electrons
Stretching
electrons

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Takamuku, Shota ; Kitagawa, Yasutaka ; Nagami, Takanori ; Fujiyoshi, Jun Ya ; Champagne, Benoît ; Nakano, Masayoshi. / Origin of the Enhancement of the Second Hyperpolarizabilities of Metal-Carbon Bonds. Dans: Journal of physical chemistry A. 2016 ; Vol 120, Numéro 34. p. 6838-6848.
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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.",
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Origin of the Enhancement of the Second Hyperpolarizabilities of Metal-Carbon Bonds. / Takamuku, Shota; Kitagawa, Yasutaka; Nagami, Takanori; Fujiyoshi, Jun Ya; Champagne, Benoît; Nakano, Masayoshi.

Dans: Journal of physical chemistry A, Vol 120, Numéro 34, 01.09.2016, p. 6838-6848.

Résultats de recherche: Contribution à un journal/une revueArticle

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