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Title: The collisional depolarization of OH(A {sup 2}Σ{sup +}) and NO(A {sup 2}Σ{sup +}) with Kr

Quantum beat spectroscopy has been used to measure rate coefficients at 300 K for collisional depolarization for NO(A {sup 2}Σ{sup +}) and OH(A {sup 2}Σ{sup +}) with krypton. Elastic depolarization rate coefficients have also been determined for OH(A) + Kr, and shown to make a much more significant contribution to the total depolarization rate than for NO(A) + Kr. While the experimental data for NO(A) + Kr are in excellent agreement with single surface quasiclassical trajectory (QCT) calculations carried out on the upper 2A{sup ′} potential energy surface, the equivalent QCT and quantum mechanical calculations cannot account for the experimental results for OH(A) + Kr collisions, particularly at low N. This disagreement is due to the presence of competing electronic quenching at low N, which requires a multi-surface, non-adiabatic treatment. Somewhat improved agreement with experiment is obtained by means of trajectory surface hopping calculations that include non-adiabatic coupling between the ground 1A{sup ′} and excited 2A{sup ′} states of OH(X/A) + Kr, although the theoretical depolarization cross sections still significantly overestimate those obtained experimentally.
Authors:
; ; ; ; ; ;  [1] ;  [2] ;  [3] ;  [4] ; ;  [5]
  1. The Department of Chemistry, The Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ (United Kingdom)
  2. Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742 (United States)
  3. Department of Chemistry and Biochemistry and Institute of Physical Science and Technology, University of Maryland, College Park, Maryland 20742 (United States)
  4. Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218 (United States)
  5. Departamento de Química Física, Facultad de Química, Universidad Complutense, 28040 Madrid (Spain)
Publication Date:
OSTI Identifier:
22255158
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 5; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; COLLISIONS; COUPLING; CROSS SECTIONS; DEPOLARIZATION; KRYPTON; NITRIC OXIDE; POTENTIAL ENERGY; QUENCHING; SPECTROSCOPY