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Strong geometric-phase effects in the hydrogen-exchange reaction at high collision energies : II. quasiclassical trajectory analysis

  • Recent calculations on the hydrogen-exchange reaction [Bouakline et al., J. Chem. Phys. 128, 124322 (2008)], have found strong geometric phase (GP) effects in the state-to-state differential cross-sections (DCS), at energies above the energetic minimum of the conical intersection (CI) seam, which cancel out in the integral cross-sections (ICS). In this article, we explain the origin of this cancellation and make other predictions about the nature of the reaction mechanisms at these high energies by carrying out quasiclassical trajectory (QCT) calculations. Detailed comparisons are made with the quantum results by splitting the quantum and the QCT cross-sections into contributions from reaction paths that wind in different senses around the CI and that scatter the products in the nearside and farside directions. Reaction paths that traverse one transition state (1-TS) scatter their products in just the nearside direction, whereas paths that traverse two transition states (2-TS) scatter in both the nearside and farside directions.Recent calculations on the hydrogen-exchange reaction [Bouakline et al., J. Chem. Phys. 128, 124322 (2008)], have found strong geometric phase (GP) effects in the state-to-state differential cross-sections (DCS), at energies above the energetic minimum of the conical intersection (CI) seam, which cancel out in the integral cross-sections (ICS). In this article, we explain the origin of this cancellation and make other predictions about the nature of the reaction mechanisms at these high energies by carrying out quasiclassical trajectory (QCT) calculations. Detailed comparisons are made with the quantum results by splitting the quantum and the QCT cross-sections into contributions from reaction paths that wind in different senses around the CI and that scatter the products in the nearside and farside directions. Reaction paths that traverse one transition state (1-TS) scatter their products in just the nearside direction, whereas paths that traverse two transition states (2-TS) scatter in both the nearside and farside directions. However, the nearside 2-TS products scatter into a different region of angular phase-space than the 1-TS products, which explains why the GP effects cancel out in the ICS. Analysis of the QCT results also suggests that two separate reaction mechanisms may be responsible for the 2-TS scattering at high energies.show moreshow less

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Metadaten
Author:Foudhil Bouakline, Stuart C. Althorpe, Pascal Larregaray, Laurent Bonnet
URL:http://www.informaworld.com/openurl?genre=journal&issn=0026-8976
DOI:https://doi.org/10.1080/00268971003610218
ISSN:0026-8976
Document Type:Article
Language:English
Year of first Publication:2010
Year of Completion:2010
Release Date:2017/03/25
Source:Molecular physics. - ISSN 0026-8976. - 108 (2010), 7-9, S. 969 - 980
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
Peer Review:Referiert