M. Naroznik et J. Niedzielski, RECOMBINATION OF RADICALS IN THE HIGH-PRESSURE AND HIGH-TEMPERATURE LIMIT - PART 2 - REACTION CH3+H, Journal of the Chemical Society. Faraday transactions (Print), 94(17), 1998, pp. 2541-2547
Citations number
27
Categorie Soggetti
Chemistry Physical","Physics, Atomic, Molecular & Chemical
The reaction CH3 + H is examined theoretically at high pressures and t
emperatures (T > 200 K) on the basis of adiabatic curves that describe
weak, long-range interactions between reactants. These curves are obt
ained by using available ab initio results and by solving the pertinen
t Schrodinger equation. A mechanism of radical recombination involves
the formation of weakly bound CH3...H intermediates which can be forme
d provided that the orbital momentum of the system does not exceed a t
hreshold value of [l(lim)] = 13 +/- 1. The rate constant for recombina
tion exhibits a very weak negative temperature dependence and is under
estimated compared with experiment. The contribution of direct recombi
nation involving a strongly bound complex depends on temperature. At h
igher temperatures it may exceed 50%.