title: Communication: Ro-vibrational control of chemical reactivity in H+CH₄→ H₂+CH₃: full-dimensional quantum dynamics calculations and a sudden model.
abstract: The mode-selective chemistry of the title reaction is studied by full-dimensional quantum dynamics simulation on an accurate ab initio potential energy surface for vanishing total angular momentum. Using a rigorous transition state based approach and multi-configurational time-dependent Hartree wave packet propagation, initial state-selected reaction probabilities for many ro-vibrational states of methane are calculated. The theoretical results are compared with experimental trends seen in reactions of methane. An intuitive interpretation of the ro-vibrational control of the chemical reactivity provided by a sudden model based on the quantum transition state concept is discussed.
authors.affiliation: Theoretische Chemie, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25, D-33615 Bielefeld, Germany.
authors.forename: Ralph
authors.initials: R
authors.lastname: Welsch
authors.affiliation: Theoretische Chemie, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25, D-33615 Bielefeld, Germany.
authors.forename: Uwe
authors.initials: U
authors.lastname: Manthe