Polarizabilities in the condensed phase and the local fields problem: A direct reaction field formulation

摘要

A consistent derivation is given for local field factors to be used for correcting measured or calculated static (hyper)polarizabilities in the condensed phases. We show how local fields should be used in the coupled perturbative Hartree-Fock or finite field methods for calculating these properties, specifically for the direct reaction field (DRF) approach, in which a quantum chemically treated "solute'' is embedded in a classical "solvent'' mainly containing discrete molecules. The derivation of the local fields is based on a strictly linear response of the classical parts and they are independent of any quantum mechanical method to be used. In applications to two water dimers in two basis sets it is shown that DRF matches fully quantum mechanical results quite well. For acetone in eleven different solvents we find that if the solvent is modeled by only a dielectric continuum (hyper)polarizabilities increase with respect to their vacuum values, while with the discrete model they decrease. We show that the use of the Lorentz field factor for extracting (hyper)polarizabilities from experimental susceptibilities may lead to serious errors. (C) 2002 American Institute of Physics. [References: 58]