Accidental conical intersections in H2Cl+(1A′)

Publisher Website
Google Scholar
Abstract
Conical intersections in Cs, C2v, and linear configurations for the 1A′ states of the H2Cl+ molecule are investigated with the help of a 10 × 10 model Hamiltonian matrix in a valence-bond basis. The line of intersection (linea) between states 2 and 3 is traced from one end point, an intersection between two states of 1B2 symmetry in a C2V configuration, to the other end point, an intersection between two 1Σ+ states in a linear H—H—Cl configuration. The linea consists of 5 branches having symmetries Cs, Cs, C∞v, C2v, and Cs. A linea between states 3 and 4 starting at a crossing of 1Σ+ and 1Π states in a linear C∞v configuration consists of three branches (Cs, C2V, Cs) leading to the asymptotic region Cl + H2. The starting point of linea 3/4 is connected to the asymptotic region H + HCl via a linea in the linear configuration. Lineae of Cs symmetry could be found by examining the eigenvalues of the Hessian matrix of second derivatives along a line of intersection in a higher symmetry (C2v or linear), a useful method for locating accidental intersections that lends itself readily to ab initio calculations. The existence of the lineae could be related to physical properties of the molecule, such as the dipole moment, indicating that the model Hamiltonian does reflect the true physical behaviour.

This publication has 0 references indexed in Scilit: