Reactive scattering of H2 from Cu(100): Six-dimensional quantum dynamics results for reaction and scattering obtained with a new, accurately fitted potential-energy surface

SOMERS, M.F.; OLSEN, R.A.; BUSNENGO, H.F.; BAERENDS, E.J.; KROES, G.J.

JOURNAL OF CHEMICAL PHYSICS

Año: 2004 vol. 121 p. 11379 - 11387

0021-9606

Six-dimensional quantum dynamical calculations are reported for the dissociative chemisorption of (v=0,1, j=0) H2 on Cu(100), and for rovibrationally inelastic scattering of (v=1, j=1) H2 fromCu(100). The dynamics results were obtained using a new potential-energy surface PES5 , which was based on density-functional calculations using a slab representation of the adsorbate-substratesystem and a generalized gradient approximation to the exchange-correlation energy. A very accurate method the corrugation reducing procedure was used to represent the density-functionaltheory data in a global potential-energy surface. With the new, more accurately fitted PES5, the agreement between the dynamics results and experimental results for reaction and rovibrationallyelastic scattering is not as good as was obtained with a previous potential-energy surface PES4, which was based on a subset of the density-functional theory data not yet including the results forthe low-symmetry Cu sites. Preliminary density-functional theory results suggest that the agreement between theory and experiment will improve over that obtained with PES5 if the density-functionalcalculations are repeated using a larger basis set and using more copper layers than employed in PES4 and PES5.