Diffusion Rates for Hydrogen on Pd(111) from Molecular Quantum Dynamics Calculations.
The van Hove formula for the dynamical structure factor (DSF) related to particle scattering at mobile adsorbates is extended to include the relaxation of the adsorbates' vibrational states. The total rate obtained from the DSF is assumed to be the sum of a diffusion and a relaxation rate. A simple kinetic model to support this assumption is presented. To illustrate its potential applicability, the formula is evaluated using wave functions, energies, and lifetimes of vibrational states obtained for H/Pd(111) from first-principle calculations. Results show that quantum effects can be expected to be important even at room temperature.
†Laboratoire de Chimie Quantique, Institut de Chimie, UMR 7177 CNRS/Université de Strasbourg, 1 rue Blaise Pascal, BP 296/R8, 67008 Strasbourg Cedex, France.
Thiago
T
Firmino
†Laboratoire de Chimie Quantique, Institut de Chimie, UMR 7177 CNRS/Université de Strasbourg, 1 rue Blaise Pascal, BP 296/R8, 67008 Strasbourg Cedex, France.
Roberto
R
Marquardt
‡CTMM, Institut Charles Gerhardt, UMR 5253 CNRS/Université de Montpellier 2, CC 1501, 34095 Montpellier Cedex 05, France.
Fabien
F
Gatti
¶Laboratoire de Chimie, UMR 5182 CNRS/Ecole Normale Supérieure de Lyon, 46 Allée d'Italie, 69364 Lyon Cedex 07, France.
Wei
W
Dong
heterogeneous catalysis; high-dimensional quantum dynamics; quantum diffusion