A combined crossed-beam, ab initio, and Rice–Ramsperger–Kassel– Marcus investigation of the reaction of carbon atoms C(3Pj) with benzene, C6H6(X 1A1g) and d6-benzene, C6D6(X 1A1g)

Autor:	Holger F. Bettinger, Jozef Peeters, Y. T. Lee, Luc Vereecken, Wesley D. Allen, Peter R. Schreiner, Henry F. Schaefer, Ina Hahndorf, Ralf I. Kaiser, P. v. R. Schleyer
Rok vydání:	2002
Předmět:	Chemistry Ab initio quantum chemistry methods Kinetic isotope effect Ab initio General Physics and Astronomy Singlet state Electronic structure Physical and Theoretical Chemistry Atomic physics Nuclear Experiment Ring (chemistry) Potential energy Chemical reaction
Zdroj:	The Journal of Chemical Physics. 116:3248-3262
ISSN:	1089-7690 0021-9606
Popis:	The reactions of atomic carbon, C(3Pj), with benzene, C6H6(X 1A1g), and with d6-benzene, C6D6(X 1A1g) were investigated at twelve collision energies between 8.8 and 52.5 kJ mol−1 using the crossed molecular beams technique. Forward-convolution fitting of the data, high-level electronic structure calculations, and Rice–Ramsperger–Kassel–Marcus (RRKM) investigations on the singlet and triplet C7H6/C7D6 potential energy hyperface suggest that at low collision energies the chemical reaction dynamics are indirect and dominated by large impact parameters. As the collision energy increases, smaller impact parameters become more important, and the chemical dynamics is increasingly direct. At all collision energies, the reaction proceeds on the triplet surface via a barrierless addition of the carbon atom to form a bicyclic intermediate followed by ring opening of the initial collision complex to a seven-membered ring intermediate (cycloheptatrienylidene). The latter decomposes without exit barrier to the thermody...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::4f7881487a8d43963426a4c8df0e3cea https://doi.org/10.1063/1.1418744 Zobrazit plný text záznamu