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

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 C2v 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 dimensionle...