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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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.
langue originaleAnglais
journalThe journal of chemical physics
Volume136
Numéro de publication2
Les DOIs
étatPublié - 14 janv. 2012

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title = "Full configuration interaction calculations of the second hyperpolarizabilities of the H4 model compound: Summation-over-states analysis and interplay with diradical characters",
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.",
author = "M. Nakano and T. Minami and H. Fukui and R. Kishi and Y. Shigeta and B. Champagne",
year = "2012",
month = "1",
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journal = "The journal of chemical physics",
issn = "0021-9606",
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Full configuration interaction calculations of the second hyperpolarizabilities of the H4 model compound : Summation-over-states analysis and interplay with diradical characters. / Nakano, M.; Minami, T.; Fukui, H.; Kishi, R.; Shigeta, Y.; Champagne, B.

Dans: The journal of chemical physics, Vol 136, Numéro 2, 14.01.2012.

Résultats de recherche: Contribution à un journal/une revueArticle

TY - JOUR

T1 - Full configuration interaction calculations of the second hyperpolarizabilities of the H4 model compound

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AU - Nakano, M.

AU - Minami, T.

AU - Fukui, H.

AU - Kishi, R.

AU - Shigeta, Y.

AU - Champagne, B.

PY - 2012/1/14

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