Proton disorder and the dielectric constant of type II clathrate hydrates

Abstract

Computational studies are presented examining the degree of proton disorder in argon and molecular hydrogen sII clathrate hydrates. Results are presented using a variety of model potentials for the dielectric constant, the proton order parameter, and the molecular volume for the clathrate systems. The dielectric constant for the clathrate systems is found to be lower than the dielectric constant of ice in all models. The ratio of the clathrate to ice dielectric constant correlates well with the ratio of the densities, which is not the case for comparisons to the liquid, so that differences in the dielectric constants between ice and the clathrates are most likely due to differences in densities. Although the computed dielectric constant is a strong function of the model potential used, the ratio of the dielectric constant of ice to that of the clathrates is insensitive to the model potential. For the nonpolar guest molecules used in the current study, the degree proton of disorder is found to depend weakly on the identity of the guest but the dielectric constant does not appear to be sensitive to pressure or the type of guest.