External Ionization Potentials of Solvated Species by Photoelectron Emission Spectroscopy

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A new technique for measuring the external ionization potentials of molecules and ions in solution has been developed. The external ionization potential can be used to obtain information the electronic energy state of solvated species and/or effects of the solvation on its electronic state.1. Reorganization energy of solvent by the photoelectron emission from thiocyanate : The external ionization energies of thiocyanate in various solvents were measured. The values can be converted to the reorganization energy of solvent. It was found that the reorganization energy well correlates with the acceptor number of the solvent.2. Alternant aromatic hydrocarbons in acetonitrile :The external ionization potentials of these solutions are smaller than those of the gaseous state. The differences are due to the polarization energies of solvent molecules around the solute molecule. The polarization energies experimentally determined do not vary in accordance with the Born equation.