Photoelectron spectroscopy of chlorine dioxide and its negative ion: a quantum dynamical study

Abstract

The photoelectron spectra of ClO₂ and its negative ion are investigated theoretically by a time-dependent wave-packet method. The near equilibrium MRCI potential energy surfaces of Peterson and Werner [J. Chem. Phys. 99, 302 (1993)] are employed in the nuclear dynamical simulations. The theoretical findings are in good agreement with the experimental results. In the experimental recording, excitations along the symmetric stretching and bending vibrational modes of ClO₂ were observed. The excitation along the asymmetric stretching vibrational mode is absent in the experimental results. Considering these observations, and utilizing the available electronic structure results, we in our dynamical study focused on the C_2v nuclear arrangements of the system. The relevant intial wave function to describe the photoelectron transition is prepared in both ways by the Hamiltonian matrix diagonalization using the ab initio potential energy surface of the ground electronic state, as well as in terms of the dimensionless normal coordinates of the electronic ground state of ClO₂. The stick vibronic spectra are calculated by solving the time-independent Schrödinger equation employing a basis set expansion approach and the Lanczos algorithm. The resulting vibrational eigenvalues are compared with the experimental results and are discussed. The inclusion of the asymmetric stretching vibration and the possible role of the nonadiabatic couplings in the nuclear dynamics are also emphasized.