Premium
Intermolecular vibrational resonance coupling: Intensity borrowing in polarized Raman spectroscopy
Author(s) -
McHale Jeanne L.
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.560400853
Subject(s) - raman spectroscopy , depolarization ratio , resonance (particle physics) , intermolecular force , dipole , chemistry , molecular physics , depolarization , rotational–vibrational coupling , molecular vibration , coherent anti stokes raman spectroscopy , coupling (piping) , atomic physics , infrared , resonance raman spectroscopy , spectroscopy , raman scattering , molecule , physics , materials science , optics , medicine , organic chemistry , quantum mechanics , metallurgy , endocrinology
Abstract The effects of solvent‐solute interactions on polarized and depolarized Raman intensity are investigated using perturbation theory, accounting for correlations in the relative orientations of the interacting transition dipoles. Two mechanisms for intensity borrowing are considered: interaction of the vibrational transition moments in the ground electronic states, and coupling of the electronic transition moments responsible for resonance Raman enhancement. The first type of interaction is shown to lead to measurable frequency shifts and depolarization ratio changes for two coupled vibrations which are infrared active and close in frequency. The second mechanism, not dependent on vibrational resonance, leads to perturbations of the depolarization ratio in resonance Raman, but not to vibrational frequency shifts.