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Electronic Quenching of OH A 2Σ+ Induced by Collisions with Kr Atoms

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
DOI:https://doi.org/10.1021/jp407035p· OSTI ID:1598548
 [1];  [2];  [3];  [3];  [4];  [5];  [5];  [6];  [6];  [6];  [6]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States); University of Pennsylvania
  2. Univ. of Pennsylvania, Philadelphia, PA (United States)
  3. Univ. of Maryland, College Park, MD (United States)
  4. Johns Hopkins Univ., Baltimore, MD (United States)
  5. Univ. Complutense Madrid (Spain)
  6. Univ. of Oxford (United Kingdom)
+ Show Author Affiliations

Electronic quenching of OH A 2Σ+ by Kr was explored through experimental studies of the collision cross sections and the OH X 2Π product state distribution. The quenching cross sections decrease with increasing rotational excitation in the excited OH A 2Σ+ electronic state. The OH X 2Π products of quenching exhibit a significant degree of rotational excitation but minimal vibrational excitation. Complementary theoretical studies of the OH (A 2Σ+, X 2Π) + Kr potential energy surfaces (PESs), nonadiabatic coupling, and quasiclassical trajectory calculations were carried out to elucidate the quenching dynamics. Accurate PESs for the two lowest diabatic states of A' symmetry were computed along with the angularly dependent coupling between them. Coupling in nearly linear HO–Kr configurations provides the mechanism for the observed electronic quenching. A deep attractive well on the OH A 2Σ+ + Kr PES facilitates access to this region of strong coupling. Furthermore, surface-hopping quasiclassical trajectory calculations yielded quenching cross sections and a OH X 2Π product rotational distribution in good accord with experimental observations.

Research Organization:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Grant/Contract Number:
FG02-87ER13792
OSTI ID:
1598548
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 50 Vol. 117; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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