title: Reaction of hydrogen with Ag(111): binding states, minimum energy paths, and kinetics.
abstract: The interaction of atomic and molecular hydrogen with the Ag(111) surface is studied using periodic density functional total-energy calculations. This paper focuses on the site preference for adsorption, ordered structures, and energy barriers for H diffusion and H recombination. Chemisorbed H atoms are unstable with respect to the H(2) molecule in all adsorption sites below monolayer coverage. The three-hollow sites are energetically the most favorable for H chemisorption. The binding energy of H to the surface decreases slightly up to one monolayer, suggesting a small repulsive H-H interaction on nonadjacent sites. Subsurface and vacancy sites are energetically less favorable for H adsorption than on-top sites. Recombination of chemisorbed H atoms leads to the formation of gas-phase H(2) with no molecular chemisorbed state. Recombination is an exothermic process and occurs on the bridge site with a pronounced energy barrier. This energy barrier is significantly higher than that inferred from experimental temperature-programmed desorption (TPD) studies. However, there is significant permeability of H atoms through the recombination energy barrier at low temperatures, thus increasing the rate constant for H(2) desorption due to quantum tunneling effects, and improving the agreement between experiment and theory.
authors.affiliation: School of Chemical and Biomolecular Engineering, The University of Sydney, Sydney, NSW 2006, Australia. a.montoya@usyd.edu.au
authors.forename: Alejandro
authors.initials: A
authors.lastname: Montoya
authors.forename: Anna
authors.initials: A
authors.lastname: Schlunke
authors.forename: Brian S
authors.initials: BS
authors.lastname: Haynes