Raman noncoincidence effect: A spectroscopic manifestation of the intermolecular vibrational coupling in dipolar molecular liquids

Abstract

Abstract This lecture addresses the analysis of the noncoincidence effect (NCE), a spectroscopic manifestation of the intermolecular coupling in molecular liquids. The vibrational bandshapes of molecular groups like C=O (strongly active in the IR spectrum) in dipolar liquids exhibit this phenomenon at a rather large extent. It will be shown that the vibrational exciton approach, developed under the assumption of the transition dipole coupling (TDC) mechanism, predicts how the orientational structure of the molecular liquid determines the magnitude and sign of the NCE. Specifically, it predicts that in simple molecular liquids, solely structured by dipolar forces, the NCE is large and positive, whereas when liquid structures are dominated by non-dipolar forces (as those present in H-bonded liquids), this scenario dramatically changes and IR-active modes may give rise to negative NCEs. This lecture is intended to offer a general overview of NCEs observed in dipolar (simple and structured) liquids in different thermodynamic conditions and of the theoretical and simulation results that assisted in their interpretation.