Theoretical study of photochemical reactions: Electron assignment and the state correlation diagram

✍ Scribed by Shinichi Yamabe; Tsutomu Minato; Yoshihiro Osamura

• Book ID: 104579894
• Publisher: John Wiley and Sons
• Year: 1980
• Tongue: English
• Weight: 289 KB
• Volume: 18
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/qua.560180134

✦ Synopsis

Abstract

A general way for drawing the state correlation diagram and seeking the reaction path is presented. If a high‐symmetry reacting system is given, its least‐motion path that maintains the symmetry is primarily examined. For a given state, it is judged whether the least‐motion path is symmetry allowed or forbidden. If allowed, it is called the direct process. If forbidden, the symmetry imposed on the system should be relaxed, resulting in the mixing of MO's. Then, the energy barrier of the avoided crossing for some excited states is removed and the possible reaction path is found. After this procedure, the symmetry‐allowed paths may be sought by the geometry optimization with a suitable wave function. By the use of such a procedure, the dissociation of diazomethane and (3H‐)diazirine is found to proceed via the C~s~ and C~2~ symmetries.