Water under Supercritical Conditions: Hydrogen Bonds, Polarity, and Vibrational Frequency Fluctuations from Ab Initio Simulations with a Dispersion Corrected Density Functional

Abstract

We have studied the effects of dispersion interactions on the dynamics of vibrational frequency fluctuations, hydrogen bonds, and free OD modes in supercritical heavy water at three different densities by means of ab initio molecular dynamics simulations. The vibrational spectral diffusion, as described by the frequency fluctuations, is studied through calculations of frequency time correlation of stretch modes of deuterated water, and its relations to the dynamics of hydrogen bonds and free OD modes are described. In addition, some of the other dynamical, structural, and electronic properties such as diffusion, rotational relaxation, radial distribution functions, hydrogen bond and coordination numbers, and dipole moments are also investigated from the perspectives of their variation with inclusion of dispersion interactions at varying density of the solvent. Although some changes in the structural properties are found on inclusion of dispersion corrections, no significant difference in the fluctuation dynamics of OD stretching frequencies and also in other dynamical quantities of supercritical water are found because of dispersion effects. The dynamics of water molecules under supercritical conditions is very fast compared to the corresponding dynamics under ambient conditions. The large thermal effects at such a high temperature seem to take over any relatively minor changes that might be introduced by weak dispersion interaction.