Roaming Radical Pathways for the Decomposition of Alkanes

被引：72

作者：

Harding, Lawrence B. ^{[1
]}

Klippenstein, Stephen J. ^{[1
]}

机构：

[1] Argonne Natl Lab, Chem Sci & Engn Div, Argonne, IL 60439 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2010年 / 1卷 / 20期

关键词：

CONCERTED CYCLOADDITION REACTIONS; VALENCE BOND DESCRIPTION; AB-INITIO; ORBITAL SYMMETRIES; SELECTION-RULES; WAVE-FUNCTIONS; ACETALDEHYDE; MECHANISM; PHOTODISSOCIATION; DISSOCIATION;

D O I：

10.1021/jz101160u

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：

CASPT2 calculations predict the existence of roaming radical pathways for the decomposition of propane, n-butane, isobutane and neopentane. The roaming radical paths lead to the formation of an alkane and an alkene instead of the expected radical products. The predicted barriers for the roaming radical paths lie similar to 1 kcal/mol below the corresponding radical asymptotes.

引用

页码：3016 / 3020

页数：5

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