Collection of Czechoslovak Chemical Communications - digital archive 

Abstract

A new approach is suggested and tested to calculation of solvent effect on chemical reactivity based on the statistical-thermodynamic Monte Carlo simulation of models of aqueous solutions devised by Metropolis. The results of computer experiments are presented for the following systems: F^-.26H₂O, CH₃F.26H₂O, FCH₃F^-.52H₂O, 26 H₂O, 52 H₂O at a temperature of 300 K at the conditions of canonical ensemble. The pair potentials MCY-CI (for water-water interactions) and 4-31G (for solute-water interactions) have been used. The 4-31G potentials have been derived from the SCF calculations of the interaction energies of the systems: F^-.H₂O, CH₃F.H₂O, and FCH₃F^-.H₂O. Internal energies, radial distribution functions, and snapshots of the configurations have been calculated. The calculated partial molar internal energies depend strongly on quality of the solute-water pair potentials and are overestimated with respect to experiment. On the basis of the results obtained, further possibilities of the suggested approach are discussed.