title: A density functional theory study of hydrogen adsorption in MOF-5.
abstract: Ab initio molecular dynamics in the generalized gradient approximation to density functional theory and ground-state relaxations are used to study the interaction between molecular hydrogen and the metal-organic framework with formula unit Zn4O(O2C-C6H4-CO2)3. Five symmetrically unique adsorption sites are identified, and calculations indicate that the sites with the strongest interaction with hydrogen are located near the Zn4O clusters. Twenty total adsorption sites are found around each Zn4O cluster, but after 16 of these are populated, the interaction energy at the remaining four sites falls off significantly. The adsorption of hydrogen on the pore walls creates an attractive potential well for hydrogen in the center of the pore. The effect of the framework on the physical structure and electronic structure of the organic linker is calculated, suggesting ways by which the interaction between the framework and hydrogen could be modified.
authors.affiliation: Department of Materials Science and Engineering, Massachusetts Institute of Technology, Building 13-5056, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA.
authors.forename: Tim
authors.initials: T
authors.lastname: Mueller
authors.forename: Gerbrand
authors.initials: G
authors.lastname: Ceder