title: Dissociation and recombination of D₂ on Cu(111): ab initio molecular dynamics calculations and improved analysis of desorption experiments.
abstract: Obtaining quantitative agreement between theory and experiment for dissociative adsorption of hydrogen on and associative desorption of hydrogen from Cu(111) remains challenging. Particularly troubling is the fact that theory gives values for the high energy limit to the dissociative adsorption probability that is as much as two times larger than experiment. In the present work we approach this discrepancy in three ways. First, we carry out a new analysis of the raw experimental data for D2 associatively desorbing from Cu(111). We also perform new ab initio molecular dynamics (AIMD) calculations that include effects of surface atom motion. Finally, we simulate time-of-flight (TOF) spectra from the theoretical reaction probability curves and we directly compare them to the raw experimental data. The results show that the use of more flexible functional forms for fitting the raw TOF spectra gives fits that are in slightly better agreement with the raw data and in considerably better agreement with theory, even though the theoretical reaction probabilities still achieve higher values at high energies. The mean absolute error (MAE) for the energy E0 at which the reaction probability equals half the experimental saturation value is now lower than 1 kcal/mol, the limit that defines chemical accuracy, while a MAE of 1.5 kcal/mol was previously obtained. The new AIMD results are only slightly different from the previous static surface results and in slightly better agreement with experiment.
authors.affiliation: Leiden Institute of Chemistry, Leiden University, Gorlaeus Laboratories, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
authors.forename: Francesco
authors.initials: F
authors.lastname: Nattino
authors.affiliation: Leiden Institute of Chemistry, Leiden University, Gorlaeus Laboratories, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
authors.forename: Alessandro
authors.initials: A
authors.lastname: Genova
authors.affiliation: Leiden Institute of Chemistry, Leiden University, Gorlaeus Laboratories, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
authors.forename: Marieke
authors.initials: M
authors.lastname: Guijt
authors.affiliation: Departamento de Química Módulo 13, Universitad Autónoma de Madrid, 28049 Madrid, Spain.
authors.forename: Alberto S
authors.initials: AS
authors.lastname: Muzas
authors.affiliation: Departamento de Química Módulo 13, Universitad Autónoma de Madrid, 28049 Madrid, Spain.
authors.forename: Cristina
authors.initials: C
authors.lastname: Díaz
authors.affiliation: Leiden Institute of Chemistry, Leiden University, Gorlaeus Laboratories, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Auerbach
authors.affiliation: Leiden Institute of Chemistry, Leiden University, Gorlaeus Laboratories, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
authors.forename: Geert-Jan
authors.initials: GJ
authors.lastname: Kroes
mesh_terms: D000465:Algorithms; D003300:Copper / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D011336:Probability; D013057:Spectrum Analysis; D013696:Temperature
chemical_list: D003300:Copper; D006859:Hydrogen