Computation of polarizability anisotropies for molecules in dilute solution: An approach to the local field correction

Abstract

This study shows that calculated polarizability anisotropies for molecules in solution are highly dependent on the near-molecule local-field correction, which is neglected in the Lorentz continuum local-field approximation. A direct approach that relies on a knowledge of the solute molecular structure, the liquid structure of the solvent, and density functional theory (DFT) calculation techniques, is proposed to compute the local-field correction, and consequently the apparent polarizabilities for molecules in dilute solution in nonpolar solvents. Polarizability anisotropies for a group of organic molecules in solution in carbon tetrachloride are calculated, and the results compare favorably with experimental data.