Water proton configurations in structures I, II, and H clathrate hydrate unit cells

Fumihito Takeuchi, Masaki Hiratsuka, Ryo Ohmura, Saman Alavi, Amadeu K. Sum, Kenji Yasuoka

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Abstract

Position and orientation of water protons need to be specified when the molecular simulation studies are performed for clathrate hydrates. Positions of oxygen atoms in water are experimentally determined by X-ray diffraction analysis of clathrate hydrate structures, but positions of water hydrogen atoms in the lattice are disordered. This study reports a determination of the water proton coordinates in unit cell of structure I (sI), II (sII), and H (sH) clathrate hydrates that satisfy the ice rules, have the lowest potential energy configuration for the protons, and give a net zero dipole moment. Possible proton coordinates in the unit cell were chosen by analyzing the symmetry of protons on the hexagonal or pentagonal faces in the hydrate cages and generating all possible proton distributions which satisfy the ice rules. We found that in the sI and sII unit cells, proton distributions with small net dipole moments have fairly narrow potential energy spreads of about 1 kJmol. The total Coulomb potential on a test unit charge placed in the cage center for the minimum energyminimum dipole unit cell configurations was calculated. In the sI small cages, the Coulomb potential energy spread in each class of cage is less than 0.1 kJmol, while the potential energy spread increases to values up to 6 kJmol in sH and 15 kJmol in the sII cages. The guest environments inside the cages can therefore be substantially different in the sII case. Cartesian coordinates for oxygen and hydrogen atoms in the sI, sII, and sH unit cells are reported for reference.

Original languageEnglish
Article number124504
JournalJournal of Chemical Physics
Volume138
Issue number12
DOIs
Publication statusPublished - 2013 Mar 28

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ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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