Unified Description of the Jahn-Teller Effect in Molecules with Only Cs Symmetry: Cyclohexoxy in Its Full 48-Dimensional Internal Coordinates.

Abstract

The two lowest potential energy surfaces of cyclohexoxy which are coupled by conical intersections and the spin-orbit interaction are determined in the full 48-dimensional internal coordinate space using a feedforward neural network to fit a diabatic potential energy matrix. The electronic structure data are obtained at the multireference configuration interaction with single- and double-excitation level. Underlying parallels between these coupled surfaces and those of the alkoxy radicals methoxy and isopropoxy are established. Earlier work by Dillon and Yarkony is extended. While the parallels would have been challenging to appreciate using the concept of the Jahn-Teller active modes, they are readily seen in terms of two internal modes centered at the conical intersection: g the energy difference gradient vector and h the interstate coupling gradient vector. In other words, g and h vectors provide a unified description of the Jahn-Teller effect in molecules exhibiting C3v and quasi-C3v symmetries. A spectral simulation in the full 48-vibrational-internal coordinate space is reported. This spectrum is obtained using recently developed algorithms designed to increase the size of the systems that can be treated with a time-independent vibronic coupling approach.