Thermodynamic stability of hydrogen clathrates

  1. Get@NRC: Thermodynamic stability of hydrogen clathrates (Opens in a new window)
DOIResolve DOI:
AuthorSearch for: ; Search for:
Proceedings titleProceedings of the National Academy of Sciences of the United States of America
ConferenceProceedings of PNAS : 2003
Pages1464514650; # of pages: 6
SubjectBiophysics; Chemistry, Physical; Dimerization; Hydrogen; Hydrogen Bonding; Kinetics; Macromolecular Substances; Models, Molecular; Software; Temperature; Thermodynamics; Water
AbstractThe stability of the recently characterized type II hydrogen clathrate [Mao, W. L., Mao, H.-K., Goncharov, A. F., Struzhkin, V. V., Guo, Q., et al. (2002) Science 297, 2247-2249] with respect to hydrogen occupancy is examined with a statistical mechanical model in conjunction with first-principles quantum chemistry calculations. It is found that the stability of the clathrate is mainly caused by dispersive interactions between H2 molecules and the water forming the cage walls. Theoretical analysis shows that both individual hydrogen molecules and nH2 guest clusters undergo essentially free rotations inside the clathrate cages. Calculations at the experimental conditions--2,000 bar (1 bar = 100 kPa) and 250 K confirm multiple occupancy of the clathrate cages with average occupations of 2.00 and 3.96 H2 molecules per D-5(12) (small) and H-5(12)6(4) (large) cage, respectively. The H2-H2O interactions also are responsible for the experimentally observed softening of the H[bond]H stretching modes. The clathrate is found to be thermodynamically stable at 25 bar and 150 K.
Publication date
AffiliationNational Research Council Canada; NRC Steacie Institute for Molecular Sciences
Peer reviewedNo
NPARC number12327027
Export citationExport as RIS
Report a correctionReport a correction
Record identifier271583ac-f068-44fb-b91f-952d5f59a0ab
Record created2009-09-10
Record modified2016-05-09
Bookmark and share
  • Share this page with Facebook (Opens in a new window)
  • Share this page with Twitter (Opens in a new window)
  • Share this page with Google+ (Opens in a new window)
  • Share this page with Delicious (Opens in a new window)