Approximately projected UHF Møller-Plesset calculations of the potential energy profiles for the reaction of the triplet oxygen atom with ethylene

✍ Scribed by Takayuki Fueno; Yoichi Takahara; Kizashi Yamaguchi

• Publisher: Elsevier Science
• Year: 1990
• Tongue: English
• Weight: 550 KB
• Volume: 167
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(90)87170-v

✦ Synopsis

Geometries for the CH2CH,0 diradical, both singlet and triplet, in various conformations were optimized and the unimolecular reaction paths for the lowest-lying singlet and triplet diradicals were determined by the SCF energy gradient method employing the 6-31G* basis functions. Approximately projected UHF Muller-Piesset calculations were then carried out for the relevant transition state structures, key intenmdiates and fragmentation products. It is found that both channel ( 1) leading to CHl f HCO through the singlet ('A') CH2CH20 diradical and channel (2) giving rise to CH,CHO+H through the triplet ('A" ) diradical are energetically acceptable. The branching ratio between these processes should be dependent on the rate of the intersystem crossing between the 'A' and 3A" states. '00 -8.4