Dressed adiabatic and diabatic potentials to study conical intersections for F + H2

Abstract

We follow a suggestion by Lipoff and Herschbach [Mol. Phys. 108, 1133 (2010)] and compare dressed and bare adiabatic potentials to get insight regarding the low-energy dynamics (e.g., cold reaction) taking place in molecular systems. In this particular case, we are interested to study the effect of conical intersections (ci) on the interacting atoms. For this purpose, we consider vibrational dressed adiabatic and vibrational dressed diabatic potentials in the entrance channel of reactive systems. According to our study, the most one should expect, in case of F + H(2), is a mild effect of the (1, 2) ci on its reactive/exchange process--an outcome also supported by experiment. This happens although the corresponding dressed and bare potential barriers (and the corresponding van der Waals potential wells) differ significantly from each other.

A tri-atomic Renner-Teller system entangled with Jahn-Teller conical intersections

“…25 This connection was found to be valid for all reported numerical studies of molecular systems with two quasi-isolated states. 4,[15][16][17]21(a), [26][27][28] In case the two-state system forms a Hilbert subspace the topological phase becomes an integer multiple of π (or zero). In the Introduction, we already mentioned that the necessary and sufficient condition that the diabatic potentials, formed by Eq.…”

“…(1) in Ref. 4). As is well known, the literature contains numerous studies based on these matrices in connection with various different, tri-atomic, tetra-atomic, and poly-atomic molecular systems.…”

“…This article is one additional link in a series of articles [1][2][3][4] devoted to the problem of revealing rigorous, efficient, and accurate methods to construct diabatic potential energy surfaces (PES) for multi-state, poly-atomic molecular systems. In the past, most of such articles were devoted to the calculation of diabatic PESs for limited regions in configuration space (CS), mainly, planar contours [5][6][7][8][9][10][11][12] (see also a list of studies in Ref.…”

“…In the past, most of such articles were devoted to the calculation of diabatic PESs for limited regions in configuration space (CS), mainly, planar contours [5][6][7][8][9][10][11][12] (see also a list of studies in Ref. 4). Extending the available approaches to the required chemical volume, so that studies of chemical processes can be facilitated, was and still a formidable task.…”

“…and −π /2 < θ < +π /2, respectively. 4 The planes under consideration are formed by the three atoms (a fluorine and two hydrogens in our case) and are parameterized via values of r, the inter-atomic distance of H 2 . The (R, θ ) grid points describe the polar coordinates of the F-atom with respect to the center-of-mass of the H 2 molecule on that plane.…”