Reactivity comparison of one-electron and two-electron processes

✍ Scribed by Tieh-Sheng Lee; San-Yan Chu

• Book ID: 104580905
• Publisher: John Wiley and Sons
• Year: 1983
• Tongue: English
• Weight: 409 KB
• Volume: 23
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/qua.560230232

✦ Synopsis

Abstract

The reaction activity is analyzed in terms of an electronic factor and a Franck–Condon factor, in analogy to that in problems of spectroscopy. A scheme for codifying a number of physical and chemical processes based on magnitude of the two factors is proposed. The electronic factor not only determines the topological feature of the potential surfaces, but also is capable of revealing certain clues leading to the mechanistic understanding from the type of operator involved. Based on such an analysis, it is concluded that all processes involving a one‐electron operator, either concerted or stepwise, may compete favorably with processes involving two‐electron operators. A forbidden reaction with a two‐electron process may therefore become a more efficient one‐electron process by either choosing a nonleast motion pathway, by carrying out the overall transformation stepwise, or by changing the occupation number of certain orbitals in the ionic form. The mechanisms of energy transfer in the excited state is also briefly discussed in terms of one‐electron and two‐electron processes.