New, unexpected, and dominant mechanisms in the hydrogen exchange reaction

Greaves, S.J.; Murdock, D.; Wrede, E.; Althorpe, S.C.

Abstract

A quasiclassical trajectory study of the state specific H+D-2(v=0, j=0)-> HD(v'=0, j'=0)+D reaction at a collision energy of 1.85 eV (total energy of 2.04 eV) found that the scattering is governed by two unexpected and dominant new mechanisms, and not by direct recoil as is generally assumed. The new mechanisms involve strong interaction with the sloping potential around the conical intersection, an area of the potential energy surface not previously considered to have much effect upon reactive scattering. Initial investigations indicate that more than 50% of reactive scattering could be the result of these new mechanisms at this collision energy. Features in the corresponding quantum mechanical results can be attributed to these new (classical) reaction mechanisms.

Citation

Greaves, S., Murdock, D., Wrede, E., & Althorpe, S. (2008). New, unexpected, and dominant mechanisms in the hydrogen exchange reaction. The Journal of Chemical Physics, 128(16), Article 164306. https://doi.org/10.1063/1.2902972

• Journal Article Type: Article
• Publication Date: Apr 1, 2008
• Deposit Date: Oct 30, 2012
• Publicly Available Date: Nov 2, 2012
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 128
• Issue: 16
• Article Number: 164306
• DOI: https://doi.org/10.1063/1.2902972
• Keywords: Atom-molecule reactions, Deuterium, Hydrogen neutral atoms, Potential energy surfaces, Reaction kinetics theory.
• Public URL: https://durham-repository.worktribe.com/output/1530914