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

Research output: Contribution to journalArticle


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.

Original languageEnglish
Pages (from-to)6838-6848
Number of pages11
JournalJournal of physical chemistry A
Issue number34
Publication statusPublished - 1 Sep 2016

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  • Projects

    Subvention - Professeur de recherche Francqui

    Nakano, M. & Castet, F.


    Project: Research

    PAI n°P7/05 - FS2: Functional Supramolecular Systems (FS2)

    CHAMPAGNE, B., De Vos, D., Van der Auweraer, M., Jérôme, C., Lazzaroni, R., Marin, G., Jonas, A., Du Prez, F., Vanderzande, D., Van Tendeloo, G., Van Speybroeck, V., NENON, S. & STAELENS, N.


    Project: Research

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