Full configuration interaction calculations of the second hyperpolarizabilities of the H4 model compound: Summation-over-states analysis and interplay with diradical characters

M. Nakano, T. Minami, H. Fukui, R. Kishi, Y. Shigeta, B. Champagne

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    Abstract

    The second hyperpolarizability (γ) of the one-dimensional H4 model compoundhas been calculated at the full configuration interaction level to describe its relationships with the diradical characters yi [the occupation numbers of the lowest unoccupied natural orbital (LUNO) + i] and the geometry. It is found that the system with intermediate y0 ( = 0.527) and small y1 ( = 0.178) exhibits the largest γ value [enhanced by a factor of 9 compared to that of a nearly closed-shell H4 analog (y0 = 0.099, y1 = 0.029)], where both the outer H–H distances are slightly larger than the inner one. These results provide a molecular design guideline for enhancing and controlling the third-order nonlinear optical properties of singlet multiradical linear molecular systems such as multiradical organic aggregates, supermolecular systems, and extended metal atom chains.
    Original languageEnglish
    JournalThe journal of chemical physics
    Volume136
    Issue number2
    DOIs
    Publication statusPublished - 14 Jan 2012

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