Methane clathrate: CH4 quantum rotor state dependent rattling potential

• Published in: The Journal of Chemical Physics
• Main Authors: Prager, M., Press, W.
• Format: Article in Journal/Newspaper
• Language: English
• Published: American Institute of Physics 2006
• Subjects: info:eu-repo/classification/ddc/540; J; Methane hydrate
• Online Access: https://juser.fz-juelich.de/record/57070; https://juser.fz-juelich.de/search?p=id:%22PreJuSER-57070%22

In methane hydrate the dominant peak in the density of states above 3 meV represents a rattling mode of the guest molecule CH(4) in the large ice cages. This mode shifts from 6.7 meV at T=4.5 K to T=30 K to 7.14 meV with conversion of CH(4) guest molecules into the tunneling ground state. The less symmetric angular density distribution PsiPsi(*) in the excited rotational state compared to the ground state allows the methane to fit better in the orientation dependent cage potential surface. This leads to a larger average distance to the cage-forming molecules with a weaker potential and a reduced rattling energy. A two state single particle model with characteristic rattling energies of 5.20 meV for pure T-methane and 7.3 meV for pure A-methane weighted by the population factors can fit the data.