STATISTICAL MECHANICAL CALCULATION OF INHOMOGENEOUSLY BROADENED ABSORPTION-LINE SHAPES IN SOLUTION

A general relation is derived between the inhomogeneously broadened absorption spectrum of a solute at infinite dilution in a solvent and an equilibrium free energy of solvation. This relation permits the techniques of equilibrium fluid theory to be applied to the calculation of solvation effects in absorption line shapes. A model calculation is presented in which the mean spherical approximation is used to predict the line shape of a polar solute in a polar solvent. Significant deviations from dielectric continuum theory are found. © 1990 American Chemical Society.