Computation Confirms Contraction: A Molecular Dynamics Study of Liquid Methanol, Water and a Methanol-Water Mixture

Abstract

It may be questioned whether potential models that have been developed independently for two different pure compounds would behave properly when used in computer simulations of mixtures of these compounds. Since they are optimized for the pure compounds there is no guarantee whatsoever that the terms describing the interaction between dissimilar molecules are correct. If the simulational and experimental values of several thermodynamical properties of the mixture relative to those of the pure compounds agree closely, however, this strongly indicates that no separate optimizations need be carried out for the mixtures. Here we present the results of isothermal-isobaric Molecular Dynamics simulations of liquid methanol, water and equimolar methanol-water mixtures, using simple point charge models. The potential parameters of the models for the pure liquids had been independently optimized. No adjustment of parameters was made for the mixture, but nonetheless the experimental volume contraction and excess enthalpy upon mixing were reproduced almost perfectly.