jp401205c_si_001.pdf (462.45 kB)
Seams of Conical Intersections Relevant to the Quenching of OH(A2Σ+) by Collisions with H2
journal contribution
posted on 2013-08-15, 00:00 authored by Joseph Dillon, David R. YarkonyUsing 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.