Quantum Mechanical Theory of Electrochemical Kinetics: Analysis by Electron Transfer Distance and Transition Probability
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- Sakata Tadayoshi
- Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology
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- Azuma Masashi
- Department of Applied Chemistry, College of Engineering, Osaka Institute of Technology
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Quantum mechanical theory of electrochemical kinetics based on Fermi’s golden rule was formulated by introducing the concept of electron-transfer distance. The expressions for the exchange current density and standard rate constant in electrochemistry were derived in analytical form, as well as exponential current overpotential dependence. The theory corresponds well to the electrode kinetics based on the transition state theory that is familiar at present with many electrochemists. It was applied to various kinds of electrode reactions to analyze the standard rate constants and the exchange current densities reported in past literature. The evaluated magnitudes of the electron exchange energy were very small, being in the order of 10−3–10−5 eV. This theory supports the ordinary electron-transfer mechanism due to the overlap of wave functions between the electrode and redox species, denying tunneling mechanism.
収録刊行物
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- Bulletin of the Chemical Society of Japan
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Bulletin of the Chemical Society of Japan 86 (10), 1158-1173, 2013
公益社団法人 日本化学会
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詳細情報 詳細情報について
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- CRID
- 1390282679120070144
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- NII論文ID
- 10031201272
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- NII書誌ID
- AA00580132
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- ISSN
- 13480634
- 00092673
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- NDL書誌ID
- 024925289
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- 本文言語コード
- en
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- データソース種別
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- JaLC
- NDL
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- 使用不可