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• W1569425458 abstract "We report a combined experimental and theoretical investigation of the nonreactive quenching channel resulting from electronic quenching of OH AΣ+2 by molecular hydrogen. The experiments utilize a pump-probe scheme to determine the OH XΠ2 population distribution following collisional quenching in a pulsed supersonic expansion. The pump laser excites OH AΣ+2 (ν′=0, N′=0), which has a significantly reduced fluorescence lifetime due to quenching by H2. The probe laser monitors the OH XΠ2 (ν″, N″) population via laser-induced fluorescence on various A-X transitions under single collision conditions. The experiments reveal a high degree of rotational excitation (N″) of the quenched OH XΠ2 products observed in ν″=1 and 2 as well as a pronounced propensity for quenching into the Π(A′) Λ-doublet level. These experiments have been supplemented by extensive multireference, configuration-interaction calculations aimed at exploring the topology of the relevant potential energy surfaces. Electronic quenching of OH AΣ+2 by H2 proceeds through conical intersections between two potentials of A′ reflection symmetry (in planar geometry) that correlate with the electronically excited AΣ+2 and ground XΠ2 states of OH. The conical intersections occur in high-symmetry geometries, in which the O side of OH points toward H2. Corroborating and extending earlier work of Hoffman and Yarkony [J. Chem. Phys. 113, 10091 (2000)], these calculations reveal a steep gradient away from the OH–H2 conical intersection as a function of both the OH orientation and interfragment distance. The former will give rise to a high degree of OH rotational excitation, as observed for the quenched OH XΠ2 products." @default.
• W1569425458 created "2016-06-24" @default.
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• W1569425458 date "2007-05-28" @default.
• W1569425458 modified "2023-09-27" @default.
• W1569425458 title "Electronic quenching of OH AΣ+2 radicals in single collision events with molecular hydrogen: Quantum state distribution of the OH XΠ2 products" @default.
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• W1569425458 doi "https://doi.org/10.1063/1.2730505" @default.
• W1569425458 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/17552771" @default.
• W1569425458 hasPublicationYear "2007" @default.
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