Crossed beam reaction of cyano radicals with hydrocarbon molecules. I. Chemical dynamics of cyanobenzene (C6H5CN; X 1A1) and perdeutero cyanobenzene (C6D5CN; X 1A1) formation from reaction of CN(X 2Σ+) with benzene C6H6(X 1A1g), and d6-benzene C6D6(X 1A1g)
| Autor: | A. H. H. Chang, Nadia Balucani, Henry F. Schaefer, Y. T. Lee, Oskar Asvany, S. H. Lin, Holger F. Bettinger, P. v. R. Schleyer, Ralf I. Kaiser |
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| Rok vydání: | 1999 |
| Předmět: | |
| Zdroj: | The Journal of Chemical Physics. 111:7457-7471 |
| ISSN: | 1089-7690 0021-9606 |
| Popis: | The chemical reaction dynamics to form cyanobenzene C6H5CN(X 1A1), and perdeutero cyanobenzene C6D5CN(X 1A1) via the neutral–neutral reaction of the cyano radical CN(X 2Σ+), with benzene C6H6(X 1A1g) and perdeutero benzene C6D6(X 1A1g), were investigated in crossed molecular beam experiments at collision energies between 19.5 and 34.4 kJ mol−1. The laboratory angular distributions and time-of-flight spectra of the products were recorded at mass to charge ratios m/e=103–98 and 108–98, respectively. Forward-convolution fitting of our experimental data together with electronic structure calculations (B3LYP/6−311+G**) indicate that the reaction is without entrance barrier and governed by an initial attack of the CN radical on the carbon side to the aromatic π electron density of the benzene molecule to form a Cs symmetric C6H6CN(C6D6CN) complex. At all collision energies, the center-of-mass angular distributions are forward–backward symmetric and peak at π/2. This shape documents that the decomposing intermed... |
| Databáze: | OpenAIRE |
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