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Title: Surface-hopping trajectories for OH(A{sup 2}Σ{sup +}) + Kr: Extension to the 1A″ state

We present a new trajectory surface hopping study of the rotational energy transfer and collisional quenching of electronically excited OH(A) radicals by Kr. The trajectory surface hopping calculations include both electronic coupling between the excited 2{sup 2}A′ and ground 1{sup 2}A′ electronic states, as well as Renner-Teller and Coriolis roto-electronic couplings between the 1{sup 2}A′ and 1{sup 2}A″, and the 2{sup 2}A′ and 1{sup 2}A″ electronic states, respectively. The new calculations are shown to lead to a noticeable improvement in the agreement between theory and experiment in this system, particularly with respect to the OH(X) rotational and Λ-doublet quantum state populations, compared with a simpler two-state treatment, which only included the electronic coupling between the 2{sup 2}A′ and 1{sup 2}A′ states. Discrepancies between the predictions of theory and experiment do however remain, and could arise either due to errors in the potential energy surfaces and couplings employed, or due to the limitations in the classical treatment of non-adiabatic effects.
Authors:
; ;  [1] ; ;  [2] ;  [3]
  1. The Department of Chemistry, The Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ (United Kingdom)
  2. Departamento de Química Física, Facultad de Química, Universidad Complutense, 28040 Madrid (Spain)
  3. Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742 (United States)
Publication Date:
OSTI Identifier:
22415638
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 14; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COMPARATIVE EVALUATIONS; ELECTRONIC STRUCTURE; ENERGY TRANSFER; ERRORS; EXCITATION; HYDROXYL RADICALS; POTENTIAL ENERGY; QUANTUM STATES; QUENCHING; SURFACES