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Utilization of electron-photoejection for characterization of labile species and studies of kinetics of their reactions

Photophysics of electron photo—ejection is briefly reviewed. Direct photo—ionization, auto—ionization and biphotonic reactions are discussed. The distinction is made between processes taking place in the gas phase and those occurring in solution. In the latter case, the formation of solvated electrons is contrasted with the formation of electron—cation pairs. The various ways by which electron—photoejections provide information of spectroscopics kinetic and thermodynamic nature are illustrated by examples. Spectra of labile species were obtained by forming them in situ. This is illustrated by examples involving l,2—diphenylcyclohexene radical—anions, cis—stilbene radical—anions, and radical—anions of 1,1—diphenylethylene. Kinetics of electron attachment and of electron—transfer processes are discussed, and it is shown how the pertinent rate constants may be derived from experiments involving electron photo—ejection. This method allows also to study the equilibria of electron transfer involving labile radical anions, e.g. cis—stilbene,Na4 + trans—stilbene cis—stilbene + trans_stilbene,Na+ or l,l—diphenylethylene radical anions + biphenyl 1,1—diphenyl ethylene + biphenyl. Finally, dimerization of labile vinylideme radical anions is reviewed and the rate constants of their dimerization determined. Electron attachment to 1,1—diphenylethylene showed some interesting features. The rate of attachment is relatively slow and equilibrium constant of attachment relatively low. Both the rate and equilibrium of this process are strongly affected by the nature of the counter—ion. The equilibrium constant of attachment of the electron—lithium cation pair to l,l—diphenylethylene is lower by several orders of magnitude than that observed for the electron—cesium cation pair.