Modeling of Structure H Carbon Dioxide Clathrate Hydrates: Guest–Lattice Energies, Crystal Structure, and Pressure Dependencies

[Image: see text] We performed first-principles computations to investigate the complex interplay of molecular interaction energies in determining the lattice structure and stability of CO(2)@sH clathrate hydrates. Density functional theory computations using periodic boundary conditions were employed to characterize energetics and the key structural properties of the sH clathrate crystal under pressure, such as equilibrium lattice volume and bulk modulus. 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. Structural relaxations of the fully CO(2)-filled and empty sH unit cells yield crystal structure and lattice energies, while their compressibility parameters were derived by including the pressure dependencies. The present quantum chemistry computations suggest anisotropy in the compressibility of the sH clathrate hydrates, with the crystal being less compressible along the a-axis direction than along the c-axis one, in distinction from nearly isotropic sI and sII structures. The detailed results presented here give insight into the complex nature of the underlying guest–host interactions, checking earlier assumptions, providing critical tests, and improving estimates. Such entries may eventually lead to better predictions of thermodynamic properties and formation conditions, with a direct impact on emerging hydrate-based technologies.