The threshold energies Et of photoelectron emission by solutions (PEES) were determined for several butylamines in acetonitrile and water. The correlations between Et and gas-phase ionization potential Ip and oxidation potential Eox were found to be linear. The difference between Et and Ip originates from the electronic polarization energy of solvent molecules and the polarization energy was found to be inversely proportional to the solvation radius in accordance with the Born solvation free energy model. The Et values were also compared with Eox to discuss the reorientation relaxation of solvent molecules in the electron transfer process. The selective coverage of aqueous solution surface with amine molecule was indicated by the PEES technique.
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Watanabe et al. (1986) studied this question.
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