Peculiar Molecular Shape and Size Dependence of the Dynamics of Fluids Confined in a Small-Pore Metal-Organic Framework

Force-field-based molecular dynamics simulations were deployed to systematically explore the dynamics of confined molecules of different shapes and sizes, that is, linear (CO₂ and N₂) and spherical (CH₄) fluids, in a model small pore system, that is, the metal-organic framework SIFSIX-2-Cu-i. These computations unveil an unprecedented molecular symmetry dependence of the translational and rotational dynamics of fluids confined in channel-like nanoporous materials. In particular, this peculiar behavior is reflected by the extremely slow decay of the Legendre reorientational correlation functions of even-parity order for the linear fluids, which is associated with jump-like orientation flips, while the spherical fluid shows a very fast decay taking place on a subpicosecond time scale. Such a fundamental understanding is relevant to diverse disciplines such as in chemistry, physics, biology, and materials science, where diatomic or polyatomic molecules of different shapes/sizes diffuse through nanopores.