Bojchenko I. Many-body effects in the p-shell electron excitation and photoionization processes of conjugated organic molecules

The general many-body theory of the p-shell photoionization and multiphoton pp*-transitions in conjugated hydrocarbons is examined in detail. The main entities of the theory such as the Dyson spin-orbitals (DOs) and their generalizations are investigated within the covariant quantum chemistry. Specifically, for these objects the spin separation procedure is first solved completely and some concrete p-systems are calculated at the full-CI level. It is shown that the some DOs make their appearance when treating intermolecular charge transfer or collisional ionization processes such as the Penning effect. A new computational procedure for the reaction field acting on a molecule or its ions in dielectric medium is proposed and some simplified schemes for estimating polarization contributions into ion solvation of the conjugated cation-radicals are suggested as well.