The reaction of carbon(3P) with chloroform (CHCl3) was studied in a crossed-beam configuration. C(3P) was produced by laser ablation of graphite, and its translational energy was varied by seeding in carrier gases to investigate the reaction mechanism in two center-of-mass energy regimes: a low-energy regime of 3.2 and 5.3 kcal/mol and a high-energy regime peaked at 85 kcal/mol. The CCl reaction product was probed by laser-induced fluorescence via the A2Δ ← X2II (Δυ = O) transition. In the low-energy regime, CCl was observed to be highly rotationally excited (Trot = 1500-1800 K), and the first excited vibrational level was significantly populated. Good agreement was obtained between the experimental results and statistical estimations based on prior calculations, suggesting that the reaction proceeds through an insertion complex and that the exit channel does not exhibit distinct dynamical biases. In the high-energy regime, however, the reaction pathway is believed to involve a short-lived complex that preferably samples reactants from the broad center-of-mass energy distribution with lower collision energy components. Contributions from an abstraction mechanism cannot be ruled out.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry