Dielectric Polarization and Alignment and the Structure of Polar Fluids

Abstract

An analysis is made of the information about the structure of dense polar fluids which resides in the dielectric constant, the Kerr constant, and the nuclear magnetic resonance (NMR) quadratic electric field effect. The inadequacy of the “local‐field” model for liquids is discussed. The existence of a nonzero molecular hyperpolarizability is shown to destroy an equivalence which would otherwise exist between the Kerr and NMR experiments, and can easily account for apparent discrepancies between the reported Kerr and NMR data for nitrobenzene and nitromethane. A method is presented for removing dielectric boundary effects from statistical averages, so that the averages can be computed locally.