Solvation Effects on Polarizability of Aromatic Fluids.

Abstract

Elucidating solvation effects on polarizability in condensed phases is important for the description of the optical and dielectric behavior of high-refractive-index molecular materials. We study these effects via the polarizability model combining electronic, solvation, and vibrational contributions. The method is applied to well-characterized highly polarizable liquid precursors: benzene, naphthalene, and phenanthrene. We find that the solvation and vibrational terms are of opposite signs and cancel almost exactly for benzene, but for naphthalene and phenanthrene, a 2.5 and 5.0% decrease relative to the equilibrium electronic polarizability of the respective monomer, α1e, is predicted, respectively. The increase in electronic polarizability affects interaction polarizability of all contacts, which is the main reason for the increasing importance of solvation contribution. The calculated refractive indices agree very well with experiment for all three systems.