A molecular dynamics study of guest-host hydrogen bonding in alcohol clathrate hydrates

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

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Clathrate hydrates are typically stabilized by suitably sized hydrophobic guest molecules. However, it has been experimentally reported that isomers of amyl-alcohol C<inf>5</inf>H<inf>11</inf>OH can be enclosed into the 5<sup>12</sup>6<sup>4</sup> cages in structure II (sII) clathrate hydrates, even though the effective radii of the molecules are larger than the van der Waals radii of the cages. To reveal the mechanism of the anomalous enclathration of hydrophilic molecules, we performed ab initio and classical molecular dynamics simulations (MD) and analyzed the structure and dynamics of a guest-host hydrogen bond for sII 3-methyl-1-butanol and structure H (sH) 2-methyl-2-butanol clathrate hydrates. The simulations clearly showed the formation of guest-host hydrogen bonds and the incorporation of the O-H group of 3-methyl-1-butanol guest molecules into the framework of the sII 5<sup>12</sup>6<sup>4</sup> cages, with the remaining hydrophobic part of the amyl-alcohol molecule well accommodated into the cages. The calculated vibrational spectra of alcohol O-H bonds showed large frequency shifts due to the strong guest-host hydrogen bonding. The 2-methyl-2-butanol guests form strong hydrogen bonds with the cage water molecules in the sH clathrate, but are not incorporated into the water framework. By comparing the structures of the alcohols in the hydrate phases, the effect of the location of O-H groups in the butyl chain of the guest molecules on the crystalline structure of the clathrate hydrates is indicated.

Original languageEnglish
Pages (from-to)12639-12647
Number of pages9
JournalPhysical Chemistry Chemical Physics
Volume17
Issue number19
DOIs
Publication statusPublished - 2015 May 21

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clathrates
Hydrates
hydrates
Molecular dynamics
Hydrogen bonds
alcohols
Alcohols
molecular dynamics
Molecules
hydrogen
molecules
Pentanols
hydrogen bonds
radii
Water
Vibrational spectra
Isomers
vibrational spectra
water
frequency shift

ASJC Scopus subject areas

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

Cite this

A molecular dynamics study of guest-host hydrogen bonding in alcohol clathrate hydrates. / Hiratsuka, Masaki; Ohmura, Ryo; Sum, Amadeu K.; Alavi, Saman; Yasuoka, Kenji.

In: Physical Chemistry Chemical Physics, Vol. 17, No. 19, 21.05.2015, p. 12639-12647.

Research output: Contribution to journalArticle

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