A new mechanism for the production of highly vibrationally excited OH in the mesosphere: An ab initio study of the reactions of O2 (A ∑u+3 and A′ Δu3) +H
In an attempt to explain the observed nightglow emission from OH (v=10) in the mesosphere that has the energy greater than the exothermicity of the H+ O3 reaction, potential energy surfaces were calculated for reactions of high lying electronic states of O2 (A ∑u+3 and A′ Δu3) with atomic hydrogen H (S2) to produce the ground state products OH (Π2) +O (P3). From collinear two-dimensional scans, several adiabatic and nonadiabatic pathways have been identified. Multiconfigurational single and double excitation configuration interaction calculations show that the adiabatic pathways on a Δ4 potential surface from O2 (A′ Δ3) +H and a ∑+4 potential surface from O2 (A ∑u+3) +H are the most favorable, with the zero-point corrected barrier heights of as low as 0.191 and 0.182 eV, respectively, and the reactions are fast. The transition states for these pathways are collinear and early, and the reaction coordinate suggests that the potential energy release of ca. 3.8 eV (larger than the energy required to excite OH to v=10) is likely to favor high vibrational excitation. © 2005 American Institute of Physics.
Liu, J; Zhang, P; Morokuma, K; Sharma, RD
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