Abstract
A comparison of semiclassical and quantum versions of molecular light scattering theory at finite temperatures is presented. A general formulation of the semiclassical radiation model is developed to the point where its relationship to the corresponding QED formalism can be established: the classical scattered electric field is proportional to the same R-matrix element as that obtained from QED for the photon scattering amplitude. The result is valid for non-resonant scattering at T = 0. The semiclassical theory conventionally also inherits aspects of a classical molecular model, principally origin-dependent molecular multipole moments. Origin independent multipoles, and corresponding response functions can be defined if the theory is cast in terms of centre-of-mass and translation invariant internal coordinates. Such a choice of coordinates brings molecular light scattering theory into line with the theory of the molecular Schrödinger equation. This is illustrated for the case of a diatomic molecule. A specific application of these results of current interest is electric-field-gradient induced birefringence (EFGB) for which there are four competing theories in the literature. In this paper we examine the treatment of finite temperature effects in two semiclassical accounts of EFGB in polar molecules and identify a likely source of the discrepancy between them revealed in a recent ab initio computational study.