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Science 4 January 2008:
Vol. 319. no. 5859, pp. 72 - 75
DOI: 10.1126/science.1150602
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Reports

Nonadiabatic Interactions in the Cl + H2 Reaction Probed by ClH2- and ClD2- Photoelectron Imaging

Etienne Garand,1 Jia Zhou,1 David E. Manolopoulos,2* Millard H. Alexander,3* Daniel M. Neumark1,4*

The degree of electronic and nuclear coupling in the Cl + H2 reaction has become a vexing problem in chemical dynamics. We report slow electron velocity-map imaging (SEVI) spectra of ClH2– and ClD2–. These spectra probe the reactant valley of the neutral reaction potential energy surface, where nonadiabatic transitions responsible for reactivity of the Cl excited spin-orbit state with H2 would occur. The SEVI spectra reveal progressions in low-frequency Cl·H2 bending and stretching modes, and are compared to simulations with and without nonadiabatic couplings between the Cl spin-orbit states. Although nonadiabatic effects are small, their inclusion improves agreement with experiment. This comparison validates the theoretical treatment, especially of the nonadiabatic effects, in this critical region of the Cl + H2 reaction, and suggests strongly that these effects are minor.

1 Department of Chemistry, University of California, Berkeley, CA 94720, USA.
2 Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford OX1 3QZ, UK.
3 Department of Chemistry and Biochemistry and Institute for Physical Science and Technology, University of Maryland, College Park, MD 20742, USA.
4 Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.

* To whom correspondence should be addressed. E-mail: david.manolopoulos{at}chem.ox.ac.uk (D.E.M.); mha{at}umd.edu (M.H.A.); dneumark{at}berkeley.edu (D.M.N.)

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THIS ARTICLE HAS BEEN CITED BY OTHER ARTICLES:
Chemical Dynamics Special Feature: Theoretical studies on bimolecular reaction dynamics.
D. C. Clary (2008)
PNAS 105, 12649-12653
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Science. ISSN 0036-8075 (print), 1095-9203 (online)