Sensitivity of predicted gas hydrate occupancies on treatment of intermolecular interactions

• Published in: The Journal of chemical physics Vol. 132; no. 10; p. 104510
• Main Authors: Thomas, Caroline, Picaud, Sylvain, Ballenegger, Vincent, Mousis, Olivier
• Format: Journal Article
• Language: English
• Published: United States 14.03.2010
• ISSN: 1089-7690
• DOI: 10.1063/1.3352570

The sensitivity of gas hydrate occupancies predicted on the basis of van der Waals-Platteeuw theory is investigated, as a function of the intermolecular guest-water interaction potential model, and of the number of water molecules taken into account. Simple analytical correction terms that account for the interactions with the water molecules beyond the cutoff distance are introduced, and shown to improve significantly the convergence rate, and hence the efficiency of the computation of the Langmuir constants. The predicted cage occupancies in pure methane and pure carbon dioxide clathrates, calculated using different recent guest-water pair potentials models derived from ab initio calculations, can vary significantly depending on the model. That sensitivity becomes especially strong in the case of multiple guest clathrates. It is shown that the abundances of coenclathrated molecules in multiple guest clathrate hydrates potentially formed on the surface of Mars can vary by more than two orders of magnitude depending on the model. These results underline the strong need for experimental data on pure and multiple guest clathrate hydrates, in particular in the temperature and pressure range that are relevant in extreme environment conditions, to discriminate among the theoretical models.