Unraveling the highly overlapping òB<inf>2</inf> - B̃²A<inf>1</inf> photoelectron bands of Cl<inf>2</inf>O: Nonadiabatic effects due to conical intersection

Abstract

The highly overlapping Ã2B2-B̃2A1 photoelectron bands of dichlorine monoxide molecule were studied using the ab initio quantum dynamical methods. The coupling parameters of the Hamiltonian were derived from ab initio electronic structure results. The photoelectron bands were then calculated using this Hamiltonian by solving the eigen value equation using a quantum dynamical method and the Lanczos algorithm. The photoelectron bands revealed prominent progression of the bend vibrational mode and a weak progression for the symmetric stretch vibrational mode of the cation.