Diffusion Monte Carlo simulations of gas phase and adsorbed D₂-(H₂)_n clusters

We have computed ground state energies and analyzed radial distributions for several gas phase and adsorbed D₂(H₂)_n and HD(H₂)_n clusters. An external model potential designed to mimic ionic adsorption sites inside porous materials is used [M. Mella and E. Curotto, J. Phys. Chem. A 121, 5005 (2017)]. The isotopic substitution lowers the ground state energies by the expected amount based on the mass differences when these are compared with the energies of the pure clusters in the gas phase. A similar impact is found for adsorbed aggregates. The dissociation energy of D₂ from the adsorbed clusters is always much higher than that of H₂ from both pure and doped aggregates. Radial distributions of D₂ and H₂ are compared for both the gas phase and adsorbed species. For the gas phase clusters, two types of hydrogen-hydrogen interactions are considered: one based on the assumption that rotations and translations are adiabatically decoupled and the other based on nonisotropic four-dimensional potential. In the gas phase clusters of sufficiently large size, we find the heavier isotopomer more likely to be near the center of mass. However, there is a considerable overlap among the radial distributions of the two species. For the adsorbed clusters, we invariably find the heavy isotope located closer to the attractive interaction source than H₂, and at the periphery of the aggregate, H₂ molecules being substantially excluded from the interaction with the source. This finding rationalizes the dissociation energy results. For D₂-(H₂)_n clusters with n≥12, such preference leads to the desorption of D₂ from the aggregate, a phenomenon driven by the minimization of the total energy that can be obtained by reducing the confinement of (H₂)₁₂. The same happens for (H₂)₁₃, indicating that such an effect may be quite general and impact on the absorption of quantum species inside porous materials.