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Electron correlation and structure dependencies of the second hyperpolarizability of ethylene
Author(s) -
Yamada S.,
Nakano M.,
Nagao H.,
Yamaguchi K.
Publication year - 1999
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1999)71:2<177::aid-qua6>3.0.co;2-y
Subject(s) - hyperpolarizability , ethylene , electronic correlation , electron , correlation , computational chemistry , chemical physics , materials science , chemistry , molecular physics , physics , mathematics , quantum mechanics , molecule , organic chemistry , geometry , polarizability , catalysis
We investigated an interesting behavior in electron correlation and structure dependencies of the second hyperpolarizability (γ) of the ethylene model. The γ values of the ethylene model with plain and twisted structures were examined using various ab initio MO methods. γ was found to be largely changed depending on the rotation angle of the CH 2 group in ethylene. The rotation‐angle dependence of γ is remarkably different among Hartree–Fock and higher‐order electron‐correlation results. By applying hyperpolarizability density analysis, it was found that there are negative and positive contributions to γ and that, especially, σ electrons play an important role to determine the rotation‐angle dependence of γ at high‐order electron correlation levels. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 71: 177–183, 1999