Rovibronic photoionization dynamics of asymmetric-top molecules

Recent progress in the study of the rovibronic photoionization dynamics of polyatomic molecules is reviewed with emphasis on the photoionization dynamics of asymmetric tops. Rovibronic photoionization selection rules and propensities for angular momentum transfer upon photoionization are discussed in the framework of an orbital ionization model in which the ionization is assumed to take place out of a single determinantal electronic wavefunction. This model enables the quantitative analysis of the rotational structure of photoelectron spectra whenever the photoionization can be interpreted in a single-determinantal picture. In more complicated situations, the model can be used to identify configurational mixing in the neutral or the cationic state and to detect rovibronic interactions between the ionization channels. Various aspects of the model are illustrated by examples including studies of the photoionization and photoelectron spectra of ketene (CH2CO), ozone (O3), ethylene (C2H4) and amidogen (NH2).