The variation of the temperature of maximum density of non-polar solutes in water: insights from the pressure change in a constant volume solution process

Abstract

The effects of non-polar solutes on the temperature of maximum density (T MD) of water are revisited by means of a molecular dynamics study of TIP4P/2005 water and two examples of spherically symmetric non-polar solutes modelled by same size single Lennard-Jones sites, with weak and strong solute–water dispersive interactions. We have adopted a two-stage strategy to model the solution process at constant pressure to reduce the analysis to the description of the pressure variation in the solution process at constant volume. To this end, the Reaction Field treatment of the Coulombic forces was used so as to be able to decompose the different molecular components to the virial pressure and their spatial variation in terms of the distance to the solute molecule. In this way, we have been able to separate which factors induce the increase of water’s T MD observed for weakly interacting non-polar solutes and the decrease that occurs when the solute is strongly interacting.