Carbon Dioxide Encapsulations and Anomalous Behaviors of Assemblies With Water

Self‐assemblies of water and carbon dioxide are of relevance in the greenhouse effect and also in energy management. A systematic study of different structures from optimized geometries of assemblies of water in different proportions with carbon dioxide n H 2 O· m CO 2 ( n = 1–8, m = 1, 2) has revealed anomalous changes in interaction energies. The study has disclosed the propensity to form pentameric and heptameric hydrogen‐bonded cyclic assemblies of water that encapsulate a carbon dioxide molecule. The heptameric assembly of water molecules with included carbon dioxide provided extra stability to the water–carbon dioxide assembly. The structural effect of different schemes of weak interactions contributed to thermodynamic properties and caused deviations from a linear trend in interaction energies and associated thermodynamic parameters among the homologous series of assemblies, showing anomalous behavior.