Attachment of Hydrogen Molecules to Atomic Ions (Na+ , Cl- ): Examination of an Adiabatic Separation of the H2 Rotational Motion.

Interactions between molecular hydrogen and ions are of interest in cluster science, astrochemistry and hydrogen storage. In dynamical simulations, H2 molecules are usually modelled as point particles, an approximation that can fail for anisotropic interactions. Here, we apply an adiabatic separation of the H2 rotational motion to build effective pseudoatom-ion potentials and in turn study the properties of (H2 )n Na+ /Cl- clusters. These interaction potentials are based on high-level ab initio calculations and Improved Lennard-Jones parametrizations, while the subsequent dynamics has been performed by quantum Monte Carlo calculations. By comparisons with simulations explicitly describing the molecular rotations, it is concluded that the present adiabatic model is very adequate. Interestingly, we find differences in the cluster stabilities and coordination shells depending on the spin isomer considered (para- or ortho-H2 ), especially for the anionic clusters.

Molecular hydrogen isotope separation by a graphdiyne membrane: a quantum-mechanical study.

Graphdiyne (GDY) has emerged as a very promising two-dimensional (2D) membrane for gas separation technologies. One of the most challenging goals is the separation of deuterium (D2) and tritium (T2) from a mixture with the most abundant hydrogen isotope, H2, an achievement that would be of great value for a number of industrial and scientific applications. In this work we study the separation of hydrogen isotopes in their transport through a GDY membrane due to mass-dependent quantum effects that are enhanced by the confinement provided by its intrinsic sub-nanometric pores. A reliable improved Lennard-Jones force field, optimized on accurate ab initio calculations, has been built to describe the molecule-membrane interaction, where the molecule is treated as a pseudoatom. The quantum dynamics of the molecules impacting on the membrane along a complete set of incidence directions have been rigorously addressed by means of wave packet calculations in the 3D space, which have allowed us to obtain transmission probabilities and, in turn, permeances, as the thermal average of the molecular flux per unit pressure. The effect of the different incidence directions on the probabilities is analyzed in detail and it is concluded that restricting the simulations to a perpendicular incidence leads to reasonable results. Moreover, it is found that a simple 1D model-using a zero-point energy-corrected interaction potential-provides an excellent agreement with the 3D probailities for perpendicular incidence conditions. Finally, D2/H2 and T2/H2 selectivities are found to reach maximum values of about 6 and 21 at ≈50 and 45 K, respectively, a feature due to a balance between zero-point energy and tunneling effects in the transport dynamics. Permeances at these temperatures are below recommended values for practical applications, however, at slightly higher temperatures (77 K) they become acceptable while the selectivities preserve promising values, particularly for the separation of tritium.