Oxidation and reduction potentials and electron-transfer interactions in photoexcited states.
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概要
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In this paper we discuss the oxidation and reduction potentials of a solvated redoxcouple in photoexcited states, these being the extension of our foregoing theoretical treatment pertinent to the energetics of sequential electrooxidation (<I>E</I><SUB>1⁄2</SUB><SUP>oxd</SUP>) and reduction (<I>E</I><SUB>1⁄2</SUB><SUP>red</SUP>) steps. After formulating the ionization potential and electron affinity of solvated molecules by using the <I>E</I><SUB>1⁄2</SUB><SUP>oxd</SUP> and <I>E</I><SUB>1⁄2</SUB><SUP>red</SUP> values, the equations on the oxidation (<I>E</I><SUB>1⁄2·exc</SUB><SUP>oxd</SUP>) and reduction (<I>E</I><SUB>1⁄2·exc</SUB><SUP>red</SUP>) potentials in excited states are derived. From these the important relation (<I>E</I><SUB>1⁄2·exc</SUB><SUP>oxd</SUP>+<I>E</I><SUB>1⁄2·exc</SUB><SUP>red</SUP>)=(<I>E</I><SUB>1⁄2</SUB><SUP>oxd</SUP>+<I>E</I><SUB>1⁄2</SUB><SUP>red</SUP>) obtained. For the case of a benzenoid alternant hydrocarbon (BAH) the above left-hand-side summation would become constant. Also, the mutual correlation of the <I>E</I><SUB>1⁄2·exc</SUB><SUP>oxd</SUP> or <I>E</I><SUB>1⁄2·exc</SUB><SUP>red</SUP> value at <SUP>1</SUP>L<SUB>a</SUB> excited state to the <I>E</I><SUB>1⁄2·exc</SUB><SUP>red</SUP> or <I>E</I><SUB>1⁄2·exc</SUB><SUP>oxd</SUP> potential at ground state is discussed for BAH's. Finally the electron-transfer interaction between an electron donor and an electron acceptor has been considered in photoexcited states by virtue of oxidation and reduction potentials. The equation thus obtained is of the same type as that formulated semiempirically by Rehm and Weller. Our treatment provides theoretical background for the Rehm and Weller equation.
- 公益社団法人 日本化学会の論文
著者
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KANO Kenji
Gifu Pharmaceutical University
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KUBOTA Tanekazu
Gifu Pharmaceutical University
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UNO Bunji
Gifu Pharmaceutical University
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GOTO Masashi
Gifu Pharmaceutical University
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Kawakita Toshio
Gifu Pharmaceutical University
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Kubota Tanekazu
Gifu College of Pharmacy
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