Role of Intermolecular Charge Fluxes in the Hydrogen-Bond-Induced Frequency Shifts of the OH Stretching Mode of Water.

Abstract

The relation between the vibrational properties and the electrostatic situations of the vibrating functional group is useful to predict vibrational spectroscopic features based on, for example, classical molecular dynamics of liquids or biomolecular systems, but to pursue its generality or the extent of applicability, it is required to understand the mechanisms giving rise to it. Here such an analysis is carried out for the OH stretching mode of water. By examining the correlations among various (structural, vibrational, and electrostatic) properties and by analyzing the spatial characteristics of the behavior of electrons occurring upon the vibration, it is shown that the dependence of the vibrational frequency and the dipole derivative of the OH stretching mode on the electric field is not of purely electrostatic origin, and the delocalized electronic motions occurring with this mode, called intermolecular charge fluxes, related to both the dipole first and second derivatives play important roles.