Molecular Understanding of Homogeneous Nucleation of CO₂ Hydrates Using Transition Path Sampling

Carbon dioxide hydrate is a solid built from hydrogen-bond stabilized water cages that encapsulate individual CO₂ molecules. As potential candidates for reducing greenhouse gases, hydrates have attracted attention from both the industry and scientific community. Under high pressure and low temperature, hydrates are formed spontaneously from a mixture of CO₂ and water via nucleation and growth. Yet, for moderate undercooling, i.e., moderate supersaturation, studying hydrate formation with molecular simulations is very challenging due to the high nucleation barriers involved. We investigate the homogeneous nucleation mechanism of CO₂ hydrate as a function of temperature using transition path sampling (TPS), which generates ensembles of unbiased dynamical trajectories across the high barrier between the liquid and solid states. The resulting path ensembles reveal that at high driving force (low temperature), amorphous structures are predominantly formed, with 4¹5¹⁰6² cages being the most abundant. With increasing temperature, the nucleation mechanism changes, and 5¹²6² becomes the most abundant cage type, giving rise to the crystalline sI structure. Reaction coordinate analysis can reveal the most important collective variable involved in the mechanism. With increasing temperature, we observe a shift from a single feature (size of the nucleus) to a 2-dimensional (size and cage type) variable as the salient ingredient of the reaction coordinate, and then back to only the nucleus size. This finding is in line with the underlying shift from an amorphous to a crystalline nucleation channel. Modeling such complex phase transformations using transition path sampling gives unbiased insight into the molecular mechanisms toward different polymorphs, and how these are determined by thermodynamics and kinetics. This study will be beneficial for researchers aiming to produce such hydrates with different polymorphic forms.