Angular Velocity Correlation Functions and High-Frequency Dielectric Relaxation

Abstract

The angular velocity correlation function can be studied through measurements of dielectric relaxation and far‐infrared absorption. Relations between these quantities are described in this article, and the data of Davies, Pardoe, Chamberlain, and Gebbie are analyzed. Velocity correlation times are obtained for molecules in four simple liquids. Hubbard has obtained a theoretical expression linking the velocity correlation time, the orientation correlation time, and the molecular moment of inertia. This expression is experimentally verified for molecules in nonviscous liquids. Certain paradoxical predictions are found when this expression is applied to viscous liquids and solids. This article considers stochastic models for relaxation, in which the probability of molecular reorientation is modulated by fluctuations in the intermolecular environment. These stochastic models lead to orientation and velocity correlation functions that are consistent with experimental observations.