Monte Carlo simulations of copper chloride solutions at various concentrations including full 3-body correction terms

Aqueous copper chloride solutions at concentrations of 1, 3 and 5 mol kg(-1) have been investigated by means of Metropolis Monte Carlo simulations. The structural results are compared with experimental data on species formation and structure of these solutions. As pair potentials are insufficient to describe solvation phenomena correctly, three-body terms were incorporated, based on ab initio calculations for the interactions Cu2+-H2O-H2O and Cu2+-Cl--H2O. The simulations were performed with three-body correction for the Cu2+-H2O-H2O alone and with three-body corrections for both Cu2+-H2O-H2O and Cu2+-Cl--H2O. The structure of the solvated copper(II) ion is discussed in terms of radial density functions and coordination number distributions. The correction of the Cu2+-Cl--H2O interactions proved absolutely necessary to achieve reliable structural results, whereas three-body effects corresponding to Cl--Cu2+-Cl- interactions could be neglected, since in most species two chloride ions are located in trans-positions. (C) 1997 Elsevier Science B.V.