jp401205c_si_001.pdf (462.45 kB)

Seams of Conical Intersections Relevant to the Quenching of OH(A2Σ+) by Collisions with H2

Download (462.45 kB)
journal contribution
posted on 15.08.2013, 00:00 by Joseph Dillon, David R. Yarkony
Using multireference configuration interaction wave functions composed of 17–52 million configuration state functions, 18 points on the 12A–22A seam and 162 points on the 22A–32A seam of conical intersections relevant to the collisional quenching of OH­(A2Σ+) by H2 are determined and analyzed. In the vicinity of planar nuclear configurations, the former seam corresponds to a 12A′–12A″ seam of intersection and the latter corresponds to a 12A′–22A′ seam. For the previously studied 22A–32A seam, two regions not previously examined are reported: (i) an out-of-plane region that connects smoothly to the 12A′–22A′ seam for planar structures and (ii) a Rydberg region that includes D3h/C3v structures where the 22A–32A seam is a 22A′–32A′ seam for D3h structures. Some of the nonplanar points on the 22A–32A seam of conical intersection are found to have OH and H2 distances comparable to those of the reactant molecules and energies below that of the reactant asymptote. These nonplanar entrance channel conical intersections suggest new mechanisms for the quenching reaction. The Rydberg region introduces new connectivity and symmetry issues. For the 12A–22A [12A′–12A″] seam, which unlike the 22A–32A [12A′–22A′] seam cannot continuously deform from planar to nonplanar structures except through confluences, no evidence of nonplanar points on the conical intersection seam was found. The continuous conical parameters, gI,J, hI,J, sxI,J, and syI,J and the associated vectors gI,J, hI,J, and sI,J, are determined and discussed. The conical parameters are made continuous by a prescribed rotation of the degenerate wave functions. The continuity of these conical parameters makes it possible to construct a quasi-diabatic representation of the coupled adiabatic potential energy surfaces.