Clathrate hydrates are crystalline inclusion compounds wherein a water framework encages small guest atoms/molecules within its cavities. Among the others, methane clathrates are the largest fossil fuel resource still available. They can also be used to safely transport gases and can also form spontaneously under suitable conditions plugging pipelines. Understanding the crystallization mechanism is very important, and given the impossibility of experimentally identifying the atomistic path, simulations played an important role in this field. Given the large computational cost of these simulations, in addition to all-atom force fields, scientists considered coarse-grained water models. Here, we have investigated the effect of coarse-graining, as implemented in the water model mW, on the crystallization characteristics of methane clathrate in comparison with the all-atom TIP4P force field. Our analyses revealed that although the characteristics directly depending on the energetics of the water models are well reproduced, dynamical properties are off by the orders of magnitude. Being crystallization a non-equilibrium process, the altered kinetics of the process results in different characteristics of crystalline nuclei. Both TIP4P and mW water models produce methane clathrate nuclei with some amount of the less stable (in the given thermodynamic conditions) structure II phase and an excess of pentagonal dodecahedral cages over the tetrakaidecahedral ones regarding the ideal ratio in structure I. However, the dependence of this excess on the methane concentration in solution is higher with the former water model, whereas with the latter, the methane concentration in solution dependence is reduced and within the statistical error.
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We estimated the solubility of methane in mW and TIP4P water models in the two-phase liquid/gas metastable system at the simulation conditions to be and ,31 respectively. Similarly, one expects that large fluctuations allowing to achieve high local supersaturation anticipating the formation of clathrate nuclei are more likely with TIP4P than mW. Our dynamical non-equilibrium approach, with trajectories starting from phase space points consistent with prescribed methane concentrations, allows us to overcome this problem/difference between force fields, focusing on the effect of coarse-graining on the second part of the crystallization mechanism.
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To take into account the contemporary presence of sI and sII domains, the numerator is modified by considering the number of 512 cages that would be engaged with 51262 and 51264 cages in sI and sII clathrate hydrate unit cells. Indeed, the quantity reported in Fig. 7(b) is .
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