Dynamic orientational pair correlations in symmetric tops and static orientational pair correlations in anisometric molecules

Abstract

The theory describing the depolarized spectrum of light scattered from symmetric tops is re-examined. On the basis of molecular symmetry it is shown that, in the rotational diffusion limit, dynamic orientational pair correlations do not affect the depolarized spectrum of scattered light. Molecular symmetry arguments are also applied to the calculation of the depolarized spectrum of light scattered from asymmetric tops and binary solutions of symmetric tops. It is found that orientational pair correlations may affect the calculated spectrum in these two cases in a rather complex fashion. Effects which had previously been attributed to the affect of dynamic orientational correlations may actually be explained on the basis of static orientational correlations alone. The experimental data on nitrobenzene and binary solutions of hexafluorobenzene/benzene are discussed explicitly. The possibility of obtaining information about the static orientational pair correlations of more than one axis in anisometric molecules is suggested.