Electronic quenching of OH A 2Σ+ radicals in single collision events with H2 and D2: a comprehensive quantum state distribution of the OH X 2Π products

Literature Information

Publication Date 2007-11-30
DOI 10.1039/B715611A
Impact Factor 3.676
Authors

Logan P. Dempsey, Craig Murray, Patricia A. Cleary, Marsha I. Lester


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Abstract

A pump–probe laser-induced fluorescence technique has been used to examine the nascent OH X 2Π product state distribution arising from non-reactive quenching of electronically excited OH A 2Σ+ by molecular hydrogen and deuterium under single-collision conditions. The OH X 2Π products were detected in v″ = 0, 1 and 2; the distribution peaks in v″ = 0 and decreases monotonically with increasing vibrational excitation. In all vibrational levels probed, the OH X 2Π products are found to be highly rotationally excited, the distribution peaking at N″ = 15 when H2 was used as the collision partner and N″ = 17 for D2. A marked propensity for production of Π(A′) Λ-doublet levels was observed, while both OH X 2Π spin–orbit manifolds were equally populated. These observations are interpreted as dynamical signatures of the nonadiabatic passage of the OH + H2/D2 system through the seams of conical intersection that couple the excited state (2 2A′) and ground state (1 2A′) surfaces.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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