CONTINUUM SOLVATION MODELS - A NEW APPROACH TO THE PROBLEM OF SOLUTESCHARGE-DISTRIBUTION AND CAVITY BOUNDARIES

In continuum solvation models the definition of a cavity that embeds t he solute molecule leads to problems related to the portion of solute' s electronic charge lying outside its boundaries (charge tails). The c orrection strategies developed so far can be shown to work insufficien tly, since they only correct the global charge defect, but lead to con siderable local errors. The present paper will be focused on the theor etical and technical aspects of this problem, and it will present in d etail a new method which allows a very refined treatment of solute's c harge tails in the outer space; some numerical results of solutes in w ater will be shown and discussed. As further analyses, the introductio n of Pauli repulsion term will be considered, and the implications all these effects have on molecular properties, such as (hyper)polarizabi lities, numerically evaluated. The new approach has been implemented w ithin the framework of the polarizable continuum model (PCM). (C) 1997 American Institute of Physics.