Detailed Raman lineshape studies of molecular motion in liquid and solid HCl

Abstract

This paper reports the study of the Raman autocorrelation functions and molecular motion of HCl in the liquid and the paraelectric solid phases. It is shown that both the molecular reorientation and other types of interaction such as the hydrogen bonding have very important effects on influencing the time evolution of the Raman correlation functions in HCl. In contrast to the theory for weakly interacting diatomic molecules, it is pointed out that in strongly interacting molecular systems the N.M.R. T ₁ process due to the intramolecular magnetic dipole-dipole interaction will not yield the same correlation time as that deduced directly from the depolarized Raman correlation function. Despite the fact that hydrogen bonding occurs in the liquid and solid HCl, from the available Raman and N.M.R. T ₁ data it was shown that large step rotational diffusion is present; however, the diffusional process is modulated by the hydrogen bond rupture-reformation process.