Structural Stability of the CO2@sI Hydrate: a Bottom‐Up Quantum Chemistry Approach on the Guest‐Cage and Inter‐Cage Interactions

Through reliable first‐principles computations, we have demonstrated the impact of CO2 molecules enclathration on the stability of sI clathrate hydrates. Given the delicate balance between the interaction energy components (van der Waals, hydrogen bonds) present on such systems, we follow a systematic bottom‐up approach starting from the individual 512 and 51262 sI cages, up to all existing combinations of two‐adjacent sI crystal cages to evaluate how such clathrate‐like models perform on the evaluation of the guest‐host and first‐neighbors inter‐cage effects, respectively. Interaction and binding energies of the CO2 occupation of the sI cages were computed using DF‐MP2 and different DFT/DFT−D electronic structure methodologies. The performance of selected DFT functionals, together with various semi‐classical dispersion corrections schemes, were validated by comparison with reference ab initio DF‐MP2 data, as well as experimental data from x‐ray and neutron diffraction studies available. Our investigation confirms that the inclusion of the CO2 in the cage/s is an energetically favorable process, with the CO2 molecule preferring to occupy the large 51262 sI cages compared to the 512 ones. Further, the present results conclude on the rigidity of the water cages arrangements, showing the importance of the inter‐cage couplings in the cluster models under study. In particular, the guest‐cage interaction is the key factor for the preferential orientation of the captured CO2 molecules in the sI cages, while the inter‐cage interactions seems to cause minor distortions with the CO2 guest neighbors interactions do not extending beyond the large 51262 sI cages. Such findings on these clathrate‐like model systems are in accord with experimental observations, drawing a direct relevance to the structural stability of CO2@sI clathrates. First‐principles computations were employed to demonstrate the impact of carbon dioxide molecule enclathration on the stability of sI clathrate hydrates. Guest‐cage interactions and first‐neighbours inter‐cage couplings were evaluated.