Infrared Spectra of Gas Hydrates from First-Principles.

The infrared spectra of sII gas hydrates have been computed using density functional theory for the first time, at equilibrium, and under pressure. It is also the first account of a full vibrational analysis (both guest and host vibrations) for gas hydrates with hydrocarbon guest molecules. Five hydrate structures were investigated: empty, propane, isobutane, ethane-methane, and propane-methane sII hydrates. The computed IR spectra are in good agreement with available experimental and theoretical results. The OH stretching frequencies were found to increase, while the H-bond stretching and H2O libration frequencies decreased with an increase in guest size and cage occupancy and with a decrease in pressure. The H2O bending vibrations are relatively independent of guest size, cage occupancy, pressure, temperature, and crystal structure. The guest vibrational modes, especially the bending modes, also have minimal pressure dependence. We have also provided more quantitative evidence that gas hydrate material properties are defined by their hydrogen bond properties, by linking H-bond strength to Young's modulus. The results and ensuing vibrational analysis presented in this paper are a valuable contribution to the ongoing efforts into developing more accurate gas hydrate identification and characterization methods in the laboratory, in industry/nature, and even in outer space.