title: Towards bond selective chemistry from first principles: methane on metal surfaces.
abstract: Controlling bond-selective chemical reactivity is of great importance and has a broad range of applications. Here, we present a molecular dynamics study of bond selective reactivity of methane and its deuterated isotopologues (i.e., CH(4-x)D(x), x=0,1,2,3,4) on Ni(111) and Pt(111) from first principles calculations. Our simulations allow for reproducing the full C-H bond selectivity recently achieved experimentally via mode-specific vibrational excitation and explain its origin. Moreover, we also predict the hitherto unexplored influence of the molecular translational energy on such a selectivity as well as the conditions under which the full selectivity can be realized for the a priori less active C-D bond.
authors.affiliation: Laboratoire de Chimie, UMR 5182 CNRS, Ecole Normale Supérieure de Lyon, Site Jacques Monod, 46, Allée d'Italie, 69364 Lyon Cedex 07, France and College of Science, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China.
authors.forename: X J
authors.initials: XJ
authors.lastname: Shen
authors.affiliation: Grupo de Fisicoquímica en Interfases y Nanoestructuras, Instituto de Física Rosario and Universidad Nacional de Rosario, 2000 Rosario, Argentina.
authors.forename: A
authors.initials: A
authors.lastname: Lozano
authors.affiliation: Laboratoire de Chimie, UMR 5182 CNRS, Ecole Normale Supérieure de Lyon, Site Jacques Monod, 46, Allée d'Italie, 69364 Lyon Cedex 07, France.
authors.forename: W
authors.initials: W
authors.lastname: Dong
authors.affiliation: Grupo de Fisicoquímica en Interfases y Nanoestructuras, Instituto de Física Rosario and Universidad Nacional de Rosario, 2000 Rosario, Argentina.
authors.forename: H F
authors.initials: HF
authors.lastname: Busnengo
authors.affiliation: College of Science, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China.
authors.forename: X H
authors.initials: XH
authors.lastname: Yan