Article

Distortion of Host Lattice in Clathrate Hydrate as a Function of Guest Molecule and Temperature

Department of Applied Physics, Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Japan
Department of Chemistry, Graduate School of Science, Osaka University, Osaka 560-0043, Japan
Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), Tsukuba, Ibaraki 305-0801, Japan
ISIS Science Division, Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire, OX11 0QX, U.K.
J. Phys. Chem. A, 2000, 104 (46), pp 10623–10630
DOI: 10.1021/jp001313j
Publication Date (Web): October 21, 2000
Copyright © 2000 American Chemical Society

Abstract

Neutron powder diffraction data of deuterated clathrate hydrates of carbon dioxide and xenon were measured in order to investigate the effects of the motion of guest molecules on the structure of the surrounding hydrogen-bonded network. Rietveld analysis revealed that the magnitude of the thermal parameters of the host atoms of the CO2 clathrate hydrate depends strongly on the crystallographic site, while those of the Xe clathrate hydrate do not depend on the site. The host lattice structure of the Xe clathrate hydrate may be a close representation of the hypothetical empty clathrate hydrate, because of the simple spherical shape of the Xe molecule. The site dependence of the thermal parameters of the host atoms in the CO2 clathrate hydrate are attributed to the motion of the CO2 molecules in the cages. The CO2 molecule rotates anisotropically about the symmetry axis inside the tetrakaidecahedral cage. We suppose that the surrounding deuterium atoms are temporarily attracted and released by the oxygen atoms of the rotating CO2 molecule and so their thermal parameters are large. It is concluded that the interaction between the guest molecule and the surrounding host atoms is so strong that the thermal vibrations of the host atoms are affected by the motion of the guest molecules inside the cages.

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Article Views: 527 Times
Received 4 April 2000
Published online 21 October 2000
Published in print 1 November 2000
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