Abstract:
Based on the diagrammatic techniques, a theory of the imaginary part of the isotropic polarizability induced by the dipole-dipole interactions between isotropically polarizable particles is elaborated. A classification of single infrared resonances corresponding to cases of the allowed and interaction-induced absorption bands is proposed. The Dipole-Induced-Dipole (DID) diagrammatic terms causing the allowed intensity variations via the reaction-field effect are analytically summed up. The thus-derived rigorous results are in conflict with the semi-empirical Onsager–Bottcher model. For the simplest reference systems (cryogenic solutions of HCl and HBr), our numerical estimations demonstrate the reaction-field contributions to observed intensity variations of vibrational bands to be weak and to become even weaker with a growth of the solvent particle dimensions that suggests the inadequacy of the DID and Onsager–Bottcher models to experimental data.
