Depolarized Rayleigh scattering and orientational relaxation of molecules in solution. II Chloroform and nitrobenzene

Abstract

Measurements of orientational relaxation times of chloroform and nitrobenzene in a variety of solvents have been made by depolarized light scattering. At constant concentration a plot of reorientational relaxation time of nitrobenzene versus solution viscosity was found to fit a straight line with nonzero intercept. The reorientational relaxation time of both solutes increased with increasing solute concentration (at constant viscosity). For nitrobenzene and chloroform, plots of the reorientational relaxation time versus solute concentration were linear. This concentration dependence is attributed predominantly to pair correlations. The ``static'' correlation parameter f and the ``dynamic'' correlation parameter g are determined for both chloroform and nitrobenzene. The carbon‐13 spin‐lattice relaxation time (T₁) for both solutes in solution has also been determined. The reorientational relaxation time of chloroform determined by NMR agrees well with the reorientational relaxation time determined by depolarized light scattering extrapolated to zero solute concentration.