Electron transfer rates in the levich and dogonadze theory of redox reactions

✍ Scribed by W. Schmickler; W. Vielstich

• Publisher: Elsevier Science
• Year: 1973
• Tongue: English
• Weight: 489 KB
• Volume: 18
• Category: Article
• ISSN: 0013-4686
• DOI: 10.1016/0013-4686(73)85042-x

✦ Synopsis

The Levich and Dogonadze theory of redox reactions in solutions is regarded as a suitable model to discuss the nature of quantumeffects in electron transfer. In Section I the quantum mechanical framework-first order perturbation theory and the Born-Oppenheimer approximation-is reviewed; an inaccuracy in the corresponding treatment by Levich is corrected. In Section II the electron transfer rate is calculated. The result differs from the formula given by Levich; the difference becomes especially important at intermediate and at low temperatures. As a consequence quantum effects should already be observable at ordinary temperatures. It is shown that the high temperature approximation can also be obtained by a semiclassical calculation. These results are compared with the activated complex theory.