title: Differential Cross Sections for the H + D2 → HD(v' = 3, j' = 4-10) + D Reaction above the Conical Intersection.
abstract: We report rovibrationally selected differential cross sections (DCSs) of the benchmark reaction H + D2 → HD(v' = 3, j' = 4-10) + D at a collision energy of 3.26 eV, which exceeds the conical intersection of the H3 potential energy surface at 2.74 eV. We use the PHOTOLOC technique in which a fluorine excimer laser at 157.64 nm photodissociates hydrogen bromide (HBr) molecules to generate fast H atoms and the HD product is detected in a state-specific manner by resonance-enhanced multiphoton ionization. Fully converged quantum wave packet calculations were performed for this reaction at this high collision energy without inclusion of the geometric phase (GP) effect, which takes into account coupling to the first excited state of the H3 potential energy surface. Multimodal structures can be observed in most of the DCSs up to j' = 10, which is predicted by theory and also well-reproduced by experiment. The theoretically calculated DCSs are in good overall agreement with the experimental measurements, which indicates that the GP effect is not large enough that its existence can be verified experimentally at this collision energy.
authors.affiliation: Department of Chemistry, Stanford University , Stanford, California 94305-5080, United States.
authors.forename: Hong
authors.initials: H
authors.lastname: Gao
authors.affiliation: Department of Chemistry, Stanford University , Stanford, California 94305-5080, United States.
authors.forename: Mahima
authors.initials: M
authors.lastname: Sneha
authors.affiliation: Max-Born-Institute , Max-Born Strasse 2A, D-12489 Berlin, Germany.
authors.forename: Foudhil
authors.initials: F
authors.lastname: Bouakline
authors.affiliation: Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors.forename: Stuart C
authors.initials: SC
authors.lastname: Althorpe
authors.affiliation: Department of Chemistry, Stanford University , Stanford, California 94305-5080, United States.
authors.forename: Richard N
authors.initials: RN
authors.lastname: Zare