Proton Transfer in Water Polymers as a Model for Intime and Solvent-Separated Ion (20) Dressick, W. J., unpublished results. Pairs

Abstract

SCF-CNDO/2 calculations, including the continuum solvent effects via an extended version of the generalized Born formula, have been performed for H30+.-.(H20),..a-ndO H(-H 20),..-H.3O0Ht--s p.ec ies (n = 0, 1,2). The proton potential curves were calculated by both varying the position of one of the intervening protons and varying the positions of all of them simultaneously, in a chain of water molecules. The oxygen and remaining hydrogen atoms were kept fixed at several intermolecular distances. By these procedures an intime ion-pair structure and a one- and two-solvent-separated ion-pair structure were respectively generated. Qualitative results show a stabilization of the intime ion-pair structure with respect to the solvent-separated one. This effect is even more pronounced when additional water molecules are incorporated into the chain.