THE SOLVATION OF IONS IN ACETONITRILE AND ACETONE - A MOLECULAR ORNSTEIN-ZERNIKE STUDY

The solvation of alkali and halide ions in acetonitrile and acetone ha s been investigated via the molecular Ornstein-Zernike theory using th e hypernetted chain approximation. Theoretical Gibbs solvation energie s and solvation numbers are compared with experiments and numerical si mulations. The calculated single-ion solvation energies are used to ch eck the hypotheses serving to split-up the measured solvation energies of salts into their single-ion components. The solvation structure ar ound the ions is discussed in detail and shown to be strongly influenc ed by the solvent-solvent spatial correlations. The calculated interio nic potentials of mean force are presented and used to compute ion-ion association constants which are compared with experiment, The influen ce of the Lennard-Jones parameters of the ions upon the calculated pro perties is emphasized. (C) 1998 American Institute of Physics.