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Hybridization effect upon the vibrational second hyperpolarizability: An ab initio study of acetylene, ethylene, and ethane
Author(s) -
Quinet Olivier,
Champagne Benoît
Publication year - 2000
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 - 10.1002/1097-461x(2000)80:4/5<871::aid-qua37>3.0.co;2-2
Subject(s) - hyperpolarizability , acetylene , anharmonicity , ab initio , chemistry , ethylene , ab initio quantum chemistry methods , computational chemistry , molecular physics , atomic physics , physics , molecule , condensed matter physics , polarizability , organic chemistry , catalysis
The vibrational second hyperpolarizability of acetylene, ethylene, and ethane has been computed ab initio at the restricted Hartree–Fock (RHF) and second‐order Møller–Plesset (MP2) levels with inclusion of the first‐order anharmonicity contributions. It turns out that by going from sp 3 to sp carbons, [μβ] 0,0 , [μ 2 α] 1,0 , and [μ 2 α] 0,1 increase substantially whereas [α 2 ] 0,0 decreases slightly. For the intensity‐dependent refractive index (IDRI), this vibrational contribution amounts to 10–20% of the static electronic counterpart, whereas for the anisotropic Kerr constant it attains 50% in the case of C 2 H 2 . © 2000 John Wiley & Sons, Inc. Int J Quant Chem 80: 871–881, 2000