NONEQUILIBRIUM SOLVATION THEORY FOR THE POLARIZABLE CONTINUUM MODEL -A NEW FORMULATION AT THE SCF LEVEL WITH APPLICATION TO THE CASE OF THE FREQUENCY-DEPENDENT LINEAR ELECTRIC-RESPONSE FUNCTION

We present a formulation of the nonequilibrium solvation problem for t he polarizable continuum model (PCM) computational scheme. The solvent is represented by a linear and homogeneous dielectric, characterized by a partition of the medium polarization vector P into a slow and a f ast component: P = P-s + P-f. The formalism is expressed in terms of t he ''direct-BEM'' PCM procedure, exploiting the stationarity condition of the free-energy functional of the solute-solvent system in a bound ary element method (BEM) computational approach. It parallels a preced ing version [Aguilar et al., J. Chem. Phys. 98, 7375 (1993)] based on an iterative PCM procedure. The present version is more convenient for the use of the coupled perturbed Hartree-Fock formalism. The applicat ion to the evaluation of the frequency-dependent molecular polarizabil ity is presented as an example. (C) John Wiley & Sons, Inc.