Monte Carlo simulation of the OH stretching spectrum of solutions of KCl, KF, LiCl and LiF in water

Abstract

Potential energy surfaces obtained by combining semi-empirical and ab initio functions are used in Monte Carlo calculations to predict thermodynamic, structural and spectroscopic properties of 0·87 M aqueous KCl, KF, LiF solutions. Intramolecular spectra are evalated using the frozen-field local-mode method of Reimers and Watts. The calculated properties are generally in good qualitative agreement with experimental observations and are interpreted in terms of the structure-making or structure-breaking effects of the ions. An analysis of the OH stretching band is given in terms of the local environments of the individual OH oscillators.