PNNL

Abstract

Molecular dynamics simulations were carried out to investigate the structural and thermodynamic properties and variations in the dipole moments of the liquid/vapor interfaces of methanol-water mixtures. Various methanol-water compositions were simulated at room temperature. We found that methanol tends to concentrate at the interface, and the computed surface tension shows a composition dependence that is consistent with experimental measurements. The methanol molecule shows preferred orientation near the interface with the methyl group pointing into the vapor phase. The methanol in the mixture is found to have larger dipole moments than that of pure liquid methanol. The strong local field induced by the surrounding water molecules is partly the reason for this difference. The dependence of hydrogen bonding patterns between methanol and water on the interface and the composition of the mixture is also discussed in the paper.