Observation of two-step nucleation in methanehydrates
Literature Information
Jenel Vatamanu, Peter G. Kusalik
In this work we show that homogeneous nucleation of methane hydrate can, under appropriate conditions, be a very rapid process, achieved within tens of nanoseconds. In agreement with recent experimental results on different systems, we find that the nucleation of a gas hydrate crystal appears as a two-step process. It starts with the formation of disordered solid-like structures, which will then spontaneously evolve to more recognizable crystalline forms. This previously elusive first-stage state is confirmed to be post-critical in the nucleation process, and is characterized as processing reasonable short-range structure but essentially no long-range order. Its energy, molecular diffusion and local structure reflect a solid-like character, although it does exhibit mobility over longer (tens of ns) timescales. We provide insights into the controversial issue of memory effects in methane hydrates. We show that areas locally richer in methane will nucleate much more readily, and no ‘memory’ of the crystal is required for fast re-crystallization. We anticipate that much richer polycrystallinity and novel methane hydrate phases could be possible.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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