Computational density-functional approaches on finite-size and guest-lattice effects in CO@sII clathrate hydrate.

We performed first-principles computations to investigate guest-host/host-host effects on the encapsulation of the CO molecule in sII clathrate hydrates from finite-size clusters up to periodic 3D crystal lattice systems. Structural and energetic properties were first computed for the individual and first-neighbors clathrate-like sII cages, where highly accurate ab initio quantum chemical methods are available nowadays, allowing in this way the assessment of the density functional (DFT) theoretical approaches employed. The performance of exchange-correlation functionals together with recently developed dispersion-corrected schemes was evaluated in describing interactions in both short-range and long-range regions of the potential. On this basis, structural relaxations of the CO-filled and empty sII unit cells yield lattice and compressibility parameters comparable to experimental and previous theoretical values available for sII hydrates. According to these data, the CO enclathration in the sII clathrate cages is a stabilizing process, either by considering both guest-host and host-host interactions in the complete unit cell or only the guest-water energies for the individual clathrate-like sII cages. CO@sII clathrates are predicted to be stable whatever the dispersion correction applied and in the case of single cage occupancy are found to be more stable than the CO@sI structures. Our results reveal that DFT approaches could provide a good reasonable description of the underlying interactions, enabling the investigation of formation and transformation processes as a function of temperature and pressure.