Predicting thermodynamic stability of clathrate hydrates based on molecular-dynamics simulations and its confirmation by phase-equilibrium measurements

Tatsuya Miyoshi, Ryo Ohmura, Kenji Yasuoka

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9 Citations (Scopus)

Abstract

In order to establish a method to predict the formation of new clathrate hydrates under milder temperature-pressure conditions, we performed a molecular-dynamics (MD)-based free energy calculation, and then hydrate phase equilibrium measurements were done to confirm the prediction. The free energy differences are calculated for the structure-H hydrates each formed with methane and each of the following large-molecule guest substances: 2-methylbutane, 2,3-dimethylbutane, 2,2-dimethylbutane, 2,2,3-trimethybutane, and 2,2,3,3-tetramethylbutane. MD simulations were performed under a constant pressure and temperature with 6120 TIP4P water molecules, 900 OPLS-UA methane molecules, and a multisite modeled 180 OPLS-UA LMGS molecule. The results of the free energy calculation indicated the structure-H hydrate formed with 2,2,3,3-tetramethylbutane is the most stable hydrate although the relevant equilibrium pressure data were not previously reported in the literature. The experimental phase equilibrium measurement performed in the present study confirmed this prediction, thereby supporting the predictive utility of the MD-based free energy calculation.

Original languageEnglish
Pages (from-to)3799-3802
Number of pages4
JournalJournal of Physical Chemistry C
Volume111
Issue number9
DOIs
Publication statusPublished - 2007 Mar 8

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clathrates
Hydrates
Phase equilibria
hydrates
Molecular dynamics
Thermodynamic stability
Free energy
molecular dynamics
thermodynamics
free energy
Computer simulation
Molecules
Methane
simulation
molecules
methane
predictions
Temperature
temperature
Water

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

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abstract = "In order to establish a method to predict the formation of new clathrate hydrates under milder temperature-pressure conditions, we performed a molecular-dynamics (MD)-based free energy calculation, and then hydrate phase equilibrium measurements were done to confirm the prediction. The free energy differences are calculated for the structure-H hydrates each formed with methane and each of the following large-molecule guest substances: 2-methylbutane, 2,3-dimethylbutane, 2,2-dimethylbutane, 2,2,3-trimethybutane, and 2,2,3,3-tetramethylbutane. MD simulations were performed under a constant pressure and temperature with 6120 TIP4P water molecules, 900 OPLS-UA methane molecules, and a multisite modeled 180 OPLS-UA LMGS molecule. The results of the free energy calculation indicated the structure-H hydrate formed with 2,2,3,3-tetramethylbutane is the most stable hydrate although the relevant equilibrium pressure data were not previously reported in the literature. The experimental phase equilibrium measurement performed in the present study confirmed this prediction, thereby supporting the predictive utility of the MD-based free energy calculation.",
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AU - Yasuoka, Kenji

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N2 - In order to establish a method to predict the formation of new clathrate hydrates under milder temperature-pressure conditions, we performed a molecular-dynamics (MD)-based free energy calculation, and then hydrate phase equilibrium measurements were done to confirm the prediction. The free energy differences are calculated for the structure-H hydrates each formed with methane and each of the following large-molecule guest substances: 2-methylbutane, 2,3-dimethylbutane, 2,2-dimethylbutane, 2,2,3-trimethybutane, and 2,2,3,3-tetramethylbutane. MD simulations were performed under a constant pressure and temperature with 6120 TIP4P water molecules, 900 OPLS-UA methane molecules, and a multisite modeled 180 OPLS-UA LMGS molecule. The results of the free energy calculation indicated the structure-H hydrate formed with 2,2,3,3-tetramethylbutane is the most stable hydrate although the relevant equilibrium pressure data were not previously reported in the literature. The experimental phase equilibrium measurement performed in the present study confirmed this prediction, thereby supporting the predictive utility of the MD-based free energy calculation.

AB - In order to establish a method to predict the formation of new clathrate hydrates under milder temperature-pressure conditions, we performed a molecular-dynamics (MD)-based free energy calculation, and then hydrate phase equilibrium measurements were done to confirm the prediction. The free energy differences are calculated for the structure-H hydrates each formed with methane and each of the following large-molecule guest substances: 2-methylbutane, 2,3-dimethylbutane, 2,2-dimethylbutane, 2,2,3-trimethybutane, and 2,2,3,3-tetramethylbutane. MD simulations were performed under a constant pressure and temperature with 6120 TIP4P water molecules, 900 OPLS-UA methane molecules, and a multisite modeled 180 OPLS-UA LMGS molecule. The results of the free energy calculation indicated the structure-H hydrate formed with 2,2,3,3-tetramethylbutane is the most stable hydrate although the relevant equilibrium pressure data were not previously reported in the literature. The experimental phase equilibrium measurement performed in the present study confirmed this prediction, thereby supporting the predictive utility of the MD-based free energy calculation.

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