Quasi-two-dimensional quantum states of H{sub 2} in stage-2 Rb-intercalated graphite

Inelastic-incoherent-neutron scattering can be a valuable nanostructural probe of H{sub 2}-doped porous materials, provided the spectral peaks can be interpreted in terms of crystal-field-split hydrogen-molecule energy levels, which represent a signature of the local symmetry. Inelastic-neutron-scattering measurements as well as extensive theoretical analyses have been performed on stage-2 Rb-intercalated graphite (Rb-GIC), with physisorbed H{sub 2}, HD, and D{sub 2}, a layered porous system with abundant spectral peaks, to assess whether the crystal-field-state picture enables a quantitative understanding of the observed structure. Potential-energy surfaces for molecular rotational and translational motion, as well as the intermolecular interactions of hydrogen molecules in Rb-GIC, were calculated within local-density-functional theory (LDFT). Model potentials, parameterized using results of the LDFT calculations, were employed in schematic calculations of rotational and translational excited state spectra of a single physisorbed H{sub 2} molecule in Rb-GIC. Results of the analysis are basically consistent with the assignment by Stead et al. of the lowest-lying peak at 1.4 meV to a rotational-tunneling transition of an isotropic hindered-rotor oriented normal to the planes, but indicate a small azimuthal anisotropy and a lower barrier than for the isotropic case. Based on the experimental isotope shifts and the theoretically predicted states, they conclude that spectral peaks at 11 and 22 meV are most likely related to center of mass excitations