Simulation of the THF hydrate-water interfacial free energy from computer simulation

Abstract

In this work, the tetrahydrofuran (THF) hydrate-water interfacial free energy is determined at $500\text{bar}$, at one point of the univariant two-phase coexistence line of the THF hydrate, by molecular dynamics simulation. The Mold Integration-Host methodology, an extension of the original Mold Integration technique to deal with hydrate-fluid interfaces, is used to calculate the interfacial energy. Water is described using the well-known TIP4P/Ice model and THF is described using a rigid version of the TraPPE model. We have recently used the combination of these two models to accurately describe the univariant two-phase dissociation line of the THF hydrate, in a wide range of pressures, from computer simulation [J. Chem. Phys. 160, 164718 (2024)]. The THF hydrate-water interfacial free energy predicted in this work is compared with the only experimental data available in the literature. The value obtained, $27(2){\text{mJ/m}}^2$, is in excellent agreement with the experimental data taken from the literature, $24(8){\text{mJ/m}}^2$. To the best of our knowledge, this is the first time that the THF hydrate-water interfacial free energy is predicted from computer simulation. This work confirms that the Mold Integration technique can be used with confidence to predict solid-fluid interfaces of complex structures, including hydrates that exhibit sI and sII crystallographic structures.

11 pages, 6 figures

References in corpus (9)

• Canonical sampling through velocity-rescaling
• Accurate determination of crystal structures based on averaged local bond order parameters
• The mold integration method for the calculation of the crystal-fluid interfacial free energy from simulations
• Solubility of carbon dioxide in water: some useful results for hydrate nucleation
• Three-phase equilibria of hydrates from computer simulation. I. Finite-size effects in the methane hydrate
• Three-phase equilibria of hydrates from computer simulation. II. Finite-size effects in the carbon dioxide hydrate
• Three-phase equilibria of hydrates from computer simulation. III. Effect of dispersive interactions in the methane and carbon dioxide hydrates
• Effect of pressure on the carbon dioxide hydrate-water interfacial free energy along its dissociation line
• Prediction of the univariant two-phase coexistence line of the tetrahydrofuran hydrate from computer simulation

Cited by in corpus (1)

• Rotationally invariant local bond order parameters for accurate determination of hydrate structures