Direct femtosecond observation of the transient intermediate in the α‐cleavage reaction of (CH3)2CO to 2CH3+CO: Resolving the issue of concertedness

Autor:	Sang Kyu Kim, Ahmed H. Zewail, Soren Pedersen
Rok vydání:	1995
Předmět:	Chemical bond Chemistry Elementary reaction Femtosecond General Physics and Astronomy Stepwise reaction Reaction intermediate Electronic structure Physical and Theoretical Chemistry Photochemistry Antibonding molecular orbital Chemical reaction
Zdroj:	The Journal of Chemical Physics. 103:477-480
ISSN:	1089-7690 0021-9606
DOI:	10.1063/1.469614
Popis:	When a reaction involving two equivalent bonds has sufficient energy to break both of them, it can proceed by either a concerted or a stepwise mechanism. For Norrish type‐I and other reactions, this issue has been controversial since direct time resolution of the individual C–C cleavage events was not possible. Here, for the elementary α‐cleavage of acetone, we report on the femtosecond resolution of the intermediates using mass spectrometry. The results show the nonconcertedness of the reaction, provide the times for the primary and secondary C–C breakage, and indicate the role of electronic structure (σ*, antibonding impulse) and the vibrational motions involved.
Databáze:	OpenAIRE
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