State-to-State F + H2 Reaction at Etrans = 0.04088 eV: QP Decomposition, Parametrized S Matrix Incorporating Regge Poles, and Uniform Asymptotic Complex Angular Momentum Analysis of the Angular Scattering

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Abstract

We report two new contributions for understanding the quantum dynamics of the benchmark state-to-state reaction, F + H2(vi, ji, mi) → FH(vf, jf, mf) + H, where (vi, ji, mi) and (vf, jf, mf) are the initial and final vibrational, rotational, and helicity quantum numbers, respectively. We analyze product differential cross sections (DCSs) for the transitions, 000 → 300, 000 → 310, and 000 → 320, at a translational energy of 0.04088 eV using the potential energy surface of Fu-Xu-Zhang. The two new contributions are as follows: (1) We exploit the recently introduced QP decomposition of J. N. L. Connor [ J. Chem. Phys. 2013, 138, 124310 ] to transform numerical partial-wave scattering (S) matrix elements for the three transitions into parametrized (analytic) formulas, in which all terms in the three parametrized S matrices have a direct physical interpretation. In particular, they contain the positions and residues of Regge poles in the first quadrant of the complex angular momentum (CAM) plane. We obtain very close agreement between the values of the parametrized and numerical S matrix elements. (2) We then apply a uniform asymptotic Watson/CAM theory, which allows a Regge pole to be close to a saddle point. It uses the parametrized S matrices and is applied to the partial wave series (PWS) representation for the scattering amplitude to understand structure in a DCS in terms of three contributing subamplitudes. We prove using this powerful CAM theory that resonance Regge poles contribute to the small-angle scattering in the DCSs for all three transitions, with the oscillations at larger angles arising from nearside-farside interference. We obtain very good agreement between the uniform asymptotic Watson/CAM DCSs and the corresponding PWS DCSs, except for angles close to the forward and backward directions, where (as expected) the Watson/CAM formulas become nonuniform.

Bibliographical metadata

Original languageEnglish
Pages (from-to)6317-6331
Number of pages15
JournalJournal of Physical Chemistry A
Volume120
Issue number32
Early online date19 Jul 2016
DOIs
StatePublished - 19 Jul 2016