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

Abstract

Averaged local bond order parameters based on spherical harmonics, also known as Lechner and Dellago order parameters, are routinely used to determine crystal structures in molecular simulations. Among different options, the combination of the ${\overline{q}}_4$ and ${\overline{q}}_6$ parameters is one of the best choices in the literature since allows one to distinguish, not only between solid- and liquid-like particles but also between different crystallographic phases, including cubic and hexagonal phases. Recently, Algaba et al. [J. Colloid Interface Sci. 623, 354, (2022)] have used the Lechner and Dellago order parameters to distinguish hydrate- and liquid-like water molecules in the context of determining the carbon dioxide hydrate-water interfacial free energy. According to the results, the preferred combination previously mentioned is not the best option to differentiate between hydrate- and liquid-like water molecules. In this work, we revisit and extend the use of these parameters to deal with systems in which clathrate hydrates phases coexist with liquid phases of water. We consider carbon dioxide, methane, tetrahydrofuran, nitrogen, and hydrogen hydrates that exhibit sI and sII crystallographic structures. We find that the ${\overline{q}}_3$ and ${\overline{q}}_{12}$ combination is the best option possible between a large number of possible different pairs to distinguish between hydrate- and liquid-like water molecules in all cases.

18 pages, 8 figures

References in corpus (24)

• Escaping free-energy minima
• Accurate determination of crystal structures based on averaged local bond order parameters
• Sampling rare switching events in biochemical networks
• Homogeneous ice nucleation at moderate supercooling from molecular simulation
• Direct calculation of the hard-sphere crystal/melt interfacial free energy
• Temperature Dependence of the Hydrophobic Hydration and Interaction of Simple Solutes: An Examination of Five Popular Water Models
• Crystal nucleation of hard spheres using molecular dynamics, umbrella sampling and forward flux sampling: A comparison of simulation techniques
• Direct calculation of the crystal-melt interfacial free energies for continuous potentials: Application to the Lennard-Jones system
• Homogeneous ice nucleation evaluated for several water models
• The mold integration method for the calculation of the crystal-fluid interfacial free energy from simulations
• Solid-liquid interface free energy through metadynamics simulations
• Interfacial Free Energy as the Key to the Pressure-Induced Deceleration of Ice Nucleation
• Equilibrium fluid-solid coexistence of hard spheres
• A study of the ice-water interface using the TIP4P/2005 water model
• A simulation study of homogeneous ice nucleation in supercooled salty water
• Anomalous Behavior in the Nucleation of Ice at Negative Pressures
• Solubility of carbon dioxide in water: some useful results for hydrate nucleation
• Simulation of the carbon dioxide hydrate-water interfacial energy
• Direct calculation of the planar NaCl-aqueous solution interfacial free energy at the solubility limit
• Variational Umbrella Seeding for Calculating Nucleation Barriers
• Effect of pressure on the carbon dioxide hydrate-water interfacial free energy along its dissociation line
• Dissociation line and driving force for nucleation of the nitrogen hydrate from computer simulation
• Simulation of the THF hydrate-water interfacial free energy from computer simulation
• Prediction of the univariant two-phase coexistence line of the tetrahydrofuran hydrate from computer simulation

Cited by in corpus (2)

• Homogeneous nucleation rate of carbon dioxide hydrate formation under experimental condition from Seeding simulations
• Prediction of the three-phase coexistence line of the ethane hydrate from molecular simulation