Effect of guest–host interaction on Raman spectrum of a CO2 clathrate hydrate single crystal

Abstract

The polarized Raman spectra of an artificial CO2 clathrate hydrate single crystal have been measured in order to examine the crystal-orientation dependence of the Raman spectra. Since the crystal had crystallographic facets, the orientation of the crystal was determined by using the Miller indices of the facets. When the angle θ between the polarization plane of the incident laser beam and the direction of one of the 〈110〉 axes of the single crystal varied, it was observed that the intensities of the peaks, which were caused by the Fermi resonance of the symmetric stretching mode and the overtone of the bending mode of CO2, and the O–H symmetric stretching vibration mode, varied with θ. Since the tetrakaidecahedron cage in the CO2 clathrate hydrate is distorted along the 〈100〉 axis, the variations of the scattering intensities of the CO2 have been calculated by using a simple model that assumes that the CO2 rotates on the {100} plane in the tetrakaidecahedron cage. The results obtained from the experiments are consistent with the calculations made by using this model. It has been concluded that the anisotropy of the peak intensities of the CO2 show the influence of the cage geometry on the motion of the guest molecule. The anisotropy of the O–H symmetric stretching vibration mode was interpreted with a five-body structure model. As the calculation with the model was consistent with the result obtained from the experiment, it was found that the anisotropy of the peak intensity of the O–H symmetric stretching vibration mode was related to the arrangement of the water molecules. We consider that the result indicates the influence of the motion of the guest molecule on the surrounding hydrogen-bonded network.