A diradical mechanism for the addition of F-2 to ethene: A density   functional theory study

doi:10.1063/1.1711599

CORC > 北京大学 > 化学与分子工程学院

	A diradical mechanism for the addition of F-2 to ethene: A density functional theory study
	Wang, BW ; Chan, L ; Chan, SP ; Chen, ZD ; Liu, ZF
刊名	journal of chemical physics
	2004
关键词	SELECTIVE VIBRATIONAL-EXCITATION ETHYLENE FLUORINE REACTION POTENTIAL-ENERGY SURFACES CHARGE-TRANSFER COMPLEXES COUPLED-CLUSTER THEORY WALL CARBON NANOTUBES MOLECULAR FLUORINE REACTION DYNAMICS ELEMENTAL FLUORINE NITROGEN MATRIX
DOI	10.1063/1.1711599
英文摘要	The long disputed mechanism for the F-2 addition to ethene is elucidated by density functional theory calculations. With hybrid functionals and a large basis set, DFT provides an excellent description for the dissociation of ground state F-2, and a reasonable account for the F-2.C2H4 van der Waals complex, which makes it possible for the modeling of reactions between elemental fluorine and organic molecules. The attack of F-2 on ethene first produces a diradical intermediate, which then dissociates into two radicals CH2F-CH2. and F.. The first step is exothermic with a low barrier around 1.8 kcal/mol, and the exothermic energy is more than enough to overcome the barrier in the second step for the homolysis of the dangling F-F bond in the diradical, although the presence of solvents and matrices environment could stabilize the diradical. Our calculations provide a coherent framework to understand this reaction not only in the gas and solution phases, but also in the matrices environment where mode-specific enhancement is observed for the addition process induced by infrared radiation. (C) 2004 American Institute of Physics.; Physics, Atomic, Molecular & Chemical; SCI(E); EI; 6; ARTICLE; 20; 9467-9472; 120
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/255020]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Wang, BW,Chan, L,Chan, SP,et al. A diradical mechanism for the addition of F-2 to ethene: A density functional theory study[J]. journal of chemical physics,2004.
APA	Wang, BW,Chan, L,Chan, SP,Chen, ZD,&Liu, ZF.(2004).A diradical mechanism for the addition of F-2 to ethene: A density functional theory study.journal of chemical physics.
MLA	Wang, BW,et al."A diradical mechanism for the addition of F-2 to ethene: A density functional theory study".journal of chemical physics (2004).