title: Angular Scattering Dynamics of the CH4 + Cl → CH3 + HCl Reaction Using Nearside-Farside, Local Angular Momentum, and Resummation Theories.
abstract: The differential cross section (DCS) for the CH4 + Cl → CH3 + HCl reaction is studied at six total energies where all of the species are in their ground states. The scattering (S) matrix elements have been calculated by the rotating line umbrella method for a dual-level ab initio analytic potential energy surface. We make the first application to this reaction of nearside-farside (NF) and local angular momentum (LAM) techniques, including resummation orders (r) of 0, 1, 2, and 3 for the partial-wave series representation of the full scattering amplitude. We find that resummation usually cleans the NF r = 0 DCSs of unphysical oscillations, especially at small angles. This cleaning effect is typically most pronounced when changing from no resummation (r = 0) to r = 1; further resummations from r = 1 to r = 2 and from r = 2 to r = 3 have smaller effects. The NF DCS analyses show that the reaction is N-dominated at sideward and large angles, whereas at small angles there are oscillations caused by NF interference. The NF LAM analysis provides consistent and complementary information, in particular for the total angular momenta that contribute to the reaction at different scattering angles. The NF analyses also provide justification for simpler N-dominant dynamical theories such as the semiclassical optical model, which provides an explanation for the distorted mirror image effect for the moduli of the S matrix elements and the DCSs, as well as the use of a hard-sphere DCS over limited angular ranges.
authors.affiliation: School of Chemistry, The University of Manchester , Manchester M13 9PL, United Kingdom.
authors.forename: A J
authors.initials: AJ
authors.lastname: Totenhofer
authors.affiliation: School of Chemistry, The University of Manchester , Manchester M13 9PL, United Kingdom.
authors.forename: J N L
authors.initials: JN
authors.lastname: Connor
authors.affiliation: Department of Chemistry and Molecular Biology, University of Gothenburg , 41296 Gothenburg, Sweden.
authors.forename: Gunnar
authors.initials: G
authors.lastname: Nyman