CORRECTION OF CAVITY-INDUCED ERRORS IN POLARIZATION CHARGES OF CONTINUUM SOLVATION MODELS

We present a formal and numerical analysis of the errors related to th e use of molecular cavities in the continuum description of solute-sol vent electrostatic interactions. In this approximation the solvent res ponse is fully described by an apparent charge distribution induced on the cavity surface. The latter is then discretized into a set of poin t charges that are generally affected by errors of different origin bu t all depending on the definition of the cavity boundaries, and the wa y its surface is partitioned. The numerical analysis is based on resul ts obtained for a set of couples of neutral/anionic solutes obtained w ith various versions of PCM methods, exploiting different correction p rocedures, as well as with two recently developed continuum methods, c omplementing PCM. (C) 1998 John Wiley & Sons, Inc.