Conical intersections and the nonadiabatic reactions H[sub 2]O+O([sup 3]P)↔OH(A [sup 2]Σ[sup +])+OH(X [sup 2]Π)

Matsika, Spiridoula; Yarkony, David R.
August 2002
Journal of Chemical Physics;8/22/2002, Vol. 117 Issue 8, p3733
Academic Journal
In this work the reaction O(³P)+H[sub 2]O → OH(X²II) + OH(A ²Z[sup +]) and the reverse reaction were studied. ³II - ³Δ and ³II - ³Σ[sup +] conical intersection seams were found that tie two reactant-channel potential energy surfaces to the two excited state potential energy surfaces correlating with OH(X²II) + OH(A ²Σ[sup +]) products. Near their lowest energy points, which occur for collinear geometries, these accidental symmetry-allowed conical intersection seams have very similar geometries and are separated by <90 cm[sup -1]. This close proximity may reflect a three state conical intersection not required by symmetry. The conical intersection seams were shown to be accessible from both the reactant and product channels without a barrier, above any reaction endoergicity, and provide in the case of the reverse reaction for branching to either H[sub 2]O + O(³P) or OH(X²II) + OH(X²II).


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