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Van der waals modulated spectral intensities: Application to infrared absorption
Author(s) -
Linder Bruno
Publication year - 1991
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/qua.560390319
Subject(s) - van der waals force , chemistry , london dispersion force , dispersion (optics) , infrared , charge (physics) , absorption (acoustics) , charge density , intermolecular force , van der waals radius , van der waals strain , atomic physics , van der waals surface , molecular physics , physics , quantum mechanics , optics , molecule
A formulation is presented of the effects of van der Waals interaction on infrared intensities. The theory takes account of induction and dispersion interactions (including charge interpenetration) and is applicable to fluids of arbitrary density. The transition moments are developed from generalized van der Waals‐induced moments, and expressions are obtained for the adsorption coefficient in terms of generalized charge densities and charge‐density (hyper)susceptibilities. Explicit expressions are given also of the integrated absorption coefficient in terms of multipoles, and (hyper)polarizabilities and their derivates, and the usefulness of this formulationin interpreting experimental data is illustrated by several examples. The relevance of the induction and dispersion interactions to allowed and to forbidden transitions made allowed is discussed.