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	Theoretical study of the competitive decomposition and isomerization of 1-hexyl radical
	Wang, Feng1,2; Cao, Dong Bo1; Liu, Gang1,2; Ren, Jie1; Li, Yong Wang1
刊名	Theoretical chemistry accounts
	2010-05-01
卷号	126期号:1-2页码:87-98
关键词	Density functional theory Decomposition Isomerization 1-hexyl radical Rate coefficient
ISSN号	1432-881X
DOI	10.1007/s00214-009-0685-y
通讯作者	Li, yong wang(ywl@sxicc.ac.cn)
英文摘要	The ground-state potential energy surface of the 1-hexyl system, including the main decomposition and isomerization processes, has been calculated with the mpw1k, bb1k, mpwb1k, mpw1b95, bmk, m05-2x and cbs-qb3 methods. on the basis of these data, thermal rate coefficients of different reaction channels and branching ratios were then calculated using the master equation formulation at 250-2,500 k. the results clearly point out that the 1,5 h atom transfer reaction of 1-hexyl radical with exothermicity proceeds through the lowest reaction barrier, whereas the decomposition processes are thermodynamically unfavorable with large endothermicity. the temperature effect is important on the relative importance of different reactions in the 1-hexyl system. in the low-temperature range of 250-900 k, isomerization reactions, especially 1,5 h atom transfer reaction of 1-hexyl radical, are dominating and responsible for over 82.17% of all the reactions, due to their smaller reaction barriers than those of the decomposition reactions. furthermore, an equilibrium process involving the isomeric forms of the hexyl radicals appearing at relative low temperature was validated theoretically. however, isomerization and decomposition processes are kinetically competitive and simultaneously important under normal pyrolysis conditions.
WOS关键词	DENSITY-FUNCTIONAL THEORY ; ATOM-TRANSFER-REACTIONS ; THERMOCHEMICAL KINETICS ; AB-INITIO ; ALKYL RADICALS ; THERMAL-DECOMPOSITION ; HYDROGEN ABSTRACTION ; UNIMOLECULAR DECOMPOSITION ; NONCOVALENT INTERACTIONS ; SCISSION REACTIONS
WOS研究方向	Chemistry
WOS类目	Chemistry, Physical
语种	英语
出版者	SPRINGER
WOS记录号	WOS:000276912900008
内容类型	期刊论文
URI标识	http://www.corc.org.cn/handle/1471x/2410658
专题	中国科学院大学
通讯作者	Li, Yong Wang
作者单位	1.Chinese Acad Sci, State Key Lab Coal Convers, Inst Coal Chem, Taiyuan 030001, Peoples R China 2.Chinese Acad Sci, Grad Univ, Beijing 100039, Peoples R China
推荐引用方式 GB/T 7714	Wang, Feng,Cao, Dong Bo,Liu, Gang,et al. Theoretical study of the competitive decomposition and isomerization of 1-hexyl radical[J]. Theoretical chemistry accounts,2010,126(1-2):87-98.
APA	Wang, Feng,Cao, Dong Bo,Liu, Gang,Ren, Jie,&Li, Yong Wang.(2010).Theoretical study of the competitive decomposition and isomerization of 1-hexyl radical.Theoretical chemistry accounts,126(1-2),87-98.
MLA	Wang, Feng,et al."Theoretical study of the competitive decomposition and isomerization of 1-hexyl radical".Theoretical chemistry accounts 126.1-2(2010):87-98.

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