Rate Prediction for Homogeneous Nucleation of Methane Hydrate at Moderate Supersaturation Using Transition Interface Sampling

• Published in: The journal of physical chemistry. B 2020-09, Vol.124 (37), p.8099-8109
• Main Authors: Arjun, A, Bolhuis, P. G
• Format: Article
• Language: English
• Subjects: B: Liquids, Chemical and Dynamical Processes in Solution, Spectroscopy in Solution
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/acs.jpcb.0c04582

The crystallization of methane hydrates via homogeneous nucleation under natural, moderate conditions is of both industrial and scientific relevance, yet still poorly understood. Predicting the nucleation rates at such conditions is notoriously difficult due to high nucleation barriers, and requires, besides an accurate molecular model, enhanced sampling. Here, we apply the transition interface sampling technique, which efficiently computes the exact rate of nucleation by generating ensembles of unbiased dynamical trajectories crossing predefined interfaces located between the stable states. Using an accurate atomistic force field and focusing on specific conditions of 280 K and 500 bar, we compute for nucleation directly into the sI crystal phase at a rate of ∼10–17 nuclei per nanosecond per simulation volume or ∼102 nuclei per second per cm3, in agreement with consensus estimates for nearby conditions. As this is most likely fortuitous, we discuss the causes of the large differences between our results and previous simulation studies. Our work shows that it is now possible to compute rates for methane hydrates at moderate supersaturation, without relying on any assumptions other than the force field.