Predominant decay channel for superexcited organic molecules

Photoabsorption and photoionization cross sections of organic molecules are systematically compared for elucidating relation between superexcitation and ionization. The cross sections examined are of alkenes, alkanes, alcohols, and ethers in the energy range of about 2 eV above the first ionization potential. Although the photoabsorption cross sections are much different from one another, the photoionization cross sections are similar in each molecular group. This result indicates that ions are formed only through direct photoionization and most of superexcited molecules dissociate to neutral fragments. Ionization efficiency curves are calculated under the assumption of no autoionization, and they well reproduce the observed ionization curves, which mainly depend on energy difference between the first and second ionization potentials.