title: Rotational effects on the dissociation dynamics of CHD3 on Pt(111).
abstract: Dissociation of methane on metal surfaces is of high practical and fundamental interest. Therefore there is currently a big push aimed at determining the simplest dynamical model that allows the reaction dynamics to be described with quantitative accuracy using quantum dynamics. Using five-dimensional quantum dynamical and full-dimensional ab initio molecular dynamics calculations, we show that the CD3 umbrella axis of CHD3 must reorient before the molecule reaches the barrier for C-H cleavage to occur in reaction on Pt(111). This rules out the application of the rotationally sudden approximation, as explicitly shown through a comparison with calculations using this approximation. Further, we suggest that the observed umbrella swing should strongly affect the sensitivity of C-H cleavage to the initial alignment of the molecule relative to the surface as found experimentally for closely related systems. We find very large differences in reactivity for molecules pre-excited to different rotational states, particularly if these states are associated with different orientations of the C-H bond.
authors.affiliation: Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P. O. Box 9502, 2300 RA Leiden, The Netherlands. g.fuchsel@chem.leidenuniv.nl g.j.kroes@chem.leidenuniv.nl.
authors.forename: Gernot
authors.initials: G
authors.lastname: Füchsel
authors.affiliation: Chemistry Department, Queen's University, Kingston, K7L 3N6 Ontario, Canada.
authors.forename: Phillip S
authors.initials: PS
authors.lastname: Thomas
authors.affiliation: Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P. O. Box 9502, 2300 RA Leiden, The Netherlands. g.fuchsel@chem.leidenuniv.nl g.j.kroes@chem.leidenuniv.nl.
authors.forename: Jurriaan
authors.initials: J
authors.lastname: den Uyl
authors.affiliation: Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P. O. Box 9502, 2300 RA Leiden, The Netherlands. g.fuchsel@chem.leidenuniv.nl g.j.kroes@chem.leidenuniv.nl.
authors.forename: Yesim
authors.initials: Y
authors.lastname: Öztürk
authors.affiliation: Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P. O. Box 9502, 2300 RA Leiden, The Netherlands. g.fuchsel@chem.leidenuniv.nl g.j.kroes@chem.leidenuniv.nl.
authors.forename: Francesco
authors.initials: F
authors.lastname: Nattino
authors.affiliation: Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany.
authors.forename: Hans-Dieter
authors.initials: HD
authors.lastname: Meyer
authors.affiliation: Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P. O. Box 9502, 2300 RA Leiden, The Netherlands. g.fuchsel@chem.leidenuniv.nl g.j.kroes@chem.leidenuniv.nl.
authors.forename: Geert-Jan
authors.initials: GJ
authors.lastname: Kroes