Indexed on: 08 Jun '07Published on: 08 Jun '07Published in: The Journal of chemical physics
We report a combined experimental and theoretical investigation of the nonreactive quenching channel resulting from electronic quenching of OH A 2Sigma+ by molecular hydrogen. The experiments utilize a pump-probe scheme to determine the OH X 2Pi population distribution following collisional quenching in a pulsed supersonic expansion. The pump laser excites OH A 2Sigma+ (nu'=0, N'=0), which has a significantly reduced fluorescence lifetime due to quenching by H2. The probe laser monitors the OH X 2Pi (nu", 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 X 2Pi products observed in nu"=1 and 2 as well as a pronounced propensity for quenching into the Pi(A') Lambda-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 A 2Sigma+ by H2 proceeds through conical intersections between two potentials of A' reflection symmetry (in planar geometry) that correlate with the electronically excited A 2Sigma+ and ground X 2Pi 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 X 2Pi products.