Reactions of O(3P) with Alkenes: H, CH2CHO, CO, and OH Channels

Autor: Zhiyuan Min, Xuebin Wang, Robert Quandt, Richard Bersohn
Rok vydání: 1998
Předmět:
Zdroj: The Journal of Physical Chemistry A. 102:60-64
ISSN: 1520-5215
1089-5639
DOI: 10.1021/jp9730611
Popis: The H, CH2CHO, CO, and OH products of the reaction of O(3P) atom with alkenes were studied by laser-induced fluorescence (LIF) under single-collision conditions. The average kinetic energies of the H atoms were 10−12 kcal/mol. The CO and OH rotational state populations were characterized by near room temperature Boltzmann distributions. The relative LIF intensities of the various products provide vivid proof of the following mechanism for the reaction of O(3P) atoms with molecules of the form R‘RCCH2, where R‘ and R are H or an alkyl group. The O atom attaches itself to the less substituted carbon atom forming a triplet ketocarbene. There is a barrier to the release of an H atom, and the rate of release must compete with the rate of intersystem crossing. If an H atom is not released, following the intersystem crossing an H atom migrates to the adjacent C atom forming an energized aldehyde, R‘RCH−CHO. The aldehyde dissociates unimolecularly forming the pair of radicals R‘• and the substituted vinoxy •RCH−C...
Databáze: OpenAIRE