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Solvent effects in infrared spectroscopy a computational approach

 

作者: JEAN LOUIS RIVAIL DANIEL RINALDI VALERIE DILLET,  

 

期刊: Molecular Physics  (Taylor Available online 1996)
卷期: Volume 89, issue 5  

页码: 1521-1529

 

ISSN:0026-8976

 

年代: 1996

 

DOI:10.1080/002689796173327

 

出版商: Taylor & Francis Group

 

数据来源: Taylor

 

摘要:

A detailed analysis of the influence of a solvent modelled as a continuum defined by its static and high frequency dielectric constants, ε and ε∞, respectively, on the force constants of a molecule in solution is proposed. It is applied to the computation of the solvent-induced frequency shifts in the vibrational spectrum of formaldehyde. The sign and the order of magnitude of the effect are correctly predicted at the scaled Hartree–Fock, MP2 or DFT levels. The computations performed on conveniently distorted systems allow us to separate the influence of the reaction field on the molecular vibrations from the influence of anharmonicity, by means of the geometry distortion induced by the solvent. The anharmonicity contribution appears to be the major contri bution to the overall effect.

 

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