Ab initio synthesis of the ozone ultraviolet continuum

Potential energy surfaces for the ground and excited electronic states responsible for the Hartley continuum of ozone are used to obtain quadratic, cubic, and quartic force constants. Vibrational dependence of rotational constants to sixth order is calculated by perturbation theory. The spectroscopic constants enable computation of rovibronic energy levels. Overlap of ground state and excited state perturbed vibrational wave functions yield Franck–Condon factors. Electric dipole allowed rovibronic transitions are generated under the Ir representation. The entire set of results generate the ultraviolet absorption spectrum. It is shown that inclusion of anharmonic terms in the vibrational Hamiltonian has a small effect upon the final spectrum, whereas rotational broadening plays a greater role in achieving agreement with experiment.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/69598/2/JCPSA6-86-10-5329-1.pd