DIRECT FEMTOSECOND OBSERVATION OF THE TRANSIENT INTERMEDIATE IN THE ALPHA-CLEAVAGE REACTION OF (CH3)(2)CO TO 2CH(3)+CO - RESOLVING THE ISSUE OF CONCERTEDNESS

被引：138

作者：

KIM, SK

PEDERSEN, S

ZEWAIL, AH

机构：

[1] Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena

来源：

JOURNAL OF CHEMICAL PHYSICS | 1995年 / 103卷 / 01期

关键词：

D O I：

10.1063/1.469614

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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. © 1995 American Institute of Physics.

引用

页码：477 / 480

页数：4

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