SINGLE-PARTICLE AND PAIR DYNAMICAL PROPERTIES OF ACETONE–METHANOL MIXTURES CONTAINING CHARGED AND NEUTRAL SOLUTES: A MOLECULAR DYNAMICS STUDY

Abstract

The dynamical properties of acetone–methanol mixtures containing either an ionic or a neutral hydrophobic solute are investigated by means of a series of molecular dynamics simulations. The primary goal has been to study how the solute and solvent dynamical properties change with variation of composition of the mixture ranging from pure acetone to pure methanol. The variations of structure and energetics of the mixture with composition are also calculated. The diffusion coefficients of both ionic and neutral solutes are found to show nonlinear variation with composition of the mixture, although the extent of nonlinearity in the diffusion of the neutral solute is much weaker. Calculations of appropriate solute-solvent distribution functions reveal the extent and nature of selective solvation of these solute species which play a role in determining the nonideal dynamical characteristics of these solutes. The free energies of solvation of the ionic solutes are also calculated and the results are discussed in the context of their dynamical behavior. The hydrogen bond statistics and dynamics of these mixtures are also calculated over their entire composition range. The energies and lifetimes of hydrogen bonds between an acetone and a methanol molecule or between two methanol molecules are found to increase with increase of acetone mole fraction of the mixture. Residence times of methanol molecules in solvation shells of acetone and methanol are also found to follow the same trend as relaxation times. However, these pair dynamical properties show essentially linear dependence on composition, thus behave almost ideally with respect to changes in composition of the mixture.