Effects of Translational and Rotational Degrees of Freedom on the Hydration of Ionic Solutes as Seen by the Popular Water Models.

ABSTRACT

We employed molecular dynamics simulations with separate thermostats for translational and rotational temperatures in order to study the effects of these degrees of freedom on the hydration of ions. In this work we examine how water models, differing in charge distribution, respond to the rise of rotational temperature. The study shows that, with respect to the distribution of negative charge, popular water models lead to different responses upon an increase of the rotational temperature. The differences arise in hydration of cations, as the negative charge distribution on the model solvent represents the determining factor in such cases. The cation-water correlation increases with the increasing rotational temperature if negative charge is placed in (or close to) the centre of the water molecule (a typical example is the SPC water model) and decreases, when the negative charge is shifted from the centre (as in the TIP5P model of water). Because all the water models examined here have similar distributions of positive charge, they all exhibit similar trends in solvation of anions. In contrast to above, the effect of translational temperature variation is similar for all water-solute pairs; any increase in translational temperature decreases the solute-water correlations.