Cage occupancy of methane hydrates from Gibbs ensemble Monte Carlo simulations

Paul E. Brumby, Daisuke Yuhara, David T. Wu, Amadeu K. Sum, Kenji Yasuoka

Research output: Contribution to journalArticlepeer-review

35 Citations (Scopus)


Isobaric-isothermal Gibbs ensemble Monte Carlo simulations of sI methane hydrates in equilibrium with bulk methane are performed to calculate large and small cage occupancies. The OPLS united-atom Lennard-Jones potential, and a variation, are used to model methane, while the TIP4P/Ice model represents water. This model system produces systematically higher total cage occupancies than those of simulations by Henley and Lucia [1] using TIP4P-Ew water and TraPPE-UA methane. We also see higher total occupancies than those observed in prior Raman spectrometry studies by Uchida et al. [2], but find good agreement for large cage occupancies. The simulations provide comprehensive predictions of large and small cage occupancies for temperatures and pressures within the ranges 270-290 K and 20-400 bar, respectively. These predictions demonstrate the advantages of the Gibbs ensemble for the simulation of clathrate hydrates; the ability to control the temperature and pressure, while not constraining the chemical composition of the hydrate phase is the key advantage of this ensemble.

Original languageEnglish
Pages (from-to)242-248
Number of pages7
JournalFluid Phase Equilibria
Publication statusPublished - 2016 Apr 15


  • Clathrate hydrate
  • Gibbs ensemble
  • Methane
  • Monte Carlo simulation
  • Occupancy

ASJC Scopus subject areas

  • General Chemical Engineering
  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


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