title: Crystal lattice size and stability of type H clathrate hydrates with various large-molecule guest substances.
abstract: To gain a better understanding of the effects of guest molecules on the lattice and stability of type H hydrates, we performed powder X-ray diffraction (PXRD) measurements and semiempirical molecular orbital calculations. The unit cell parameters and cohesive energies of various type H hydrates that contain methane (CH4) were analyzed. PXRD measurements indicated that an increase in the large-molecule guest volume caused the unit cell volume to increase. It was also indicated that a large-molecule guest substance caused the a-axis-direction of the unit cell to increase with little decrease in the c-axis direction. Calculations of cohesive energy by means of a semiempirical molecular orbital method indicated that the functional group and configuration of large-molecule guest substances affects the stability of type H hydrates. It was concluded that the icosahedron (5(12)6(8)) cages do not easily increase in length along the c-axis direction when larger guest molecules are used to form the hydrate, but the 5(12)6(8) cage and the layer of dodecahedron (5(12)) cages can easily increase in length along the a-axis direction due to interactions of the guest-host molecule.
authors.affiliation: National Institute of Advanced Industrial Science and Technology (AIST), Central 5, 1-1-1, Higashi, Tsukuba 305-8565, Japan. s.takeya@aist.go.jp
authors.forename: Satoshi
authors.initials: S
authors.lastname: Takeya
authors.forename: Akira
authors.initials: A
authors.lastname: Hori
authors.forename: Tsutomu
authors.initials: T
authors.lastname: Uchida
authors.forename: Ryo
authors.initials: R
authors.lastname: Ohmura