Inelastic neutron scattering and molecular dynamics studies on low-frequency modes of clathrate hydrates

Low-frequency modes of gas hydrates with Xe, Ar, O₂, and N₂ atoms/molecules have been studied by inelastic neutron-scattering and molecular dynamics simulations. Type I and type II clathrate hydrates show some small but significant differences of the low-frequency host contribution to the density of states. Both differ markedly from that of ice Ih and depend only weakly on the guest. The vibrational modes associated with Xe atoms were observed at 2.2, 2.9, and 4.0 meV (T = 100 K). They are in good agreement with predictions from molecular dynamics simulations. In the case of N₂ hydrate we found a well-defined peak at about 2 meV, which shows a remarkable shift to higher frequency with increasing temperature. This peak and a broad peak that is overlapped with the host lattice modes (6.5 and 10.5 meV) are assigned to the vibration of N₂ molecules in the large and small cages, respectively. The calculated vibrational spectra of N₂ molecules in doubly occupied large cages show a significant distinct spectral distribution. The anharmonic shift of the guest atoms in large cages is significantly less pronounced in Xe hydrates suggesting that guest-host interactions can vary considerably from one system to another.