APPLICATION OF THE CANONICAL FLEXIBLE TRANSITION-STATE THEORY TO CH3,CF3, AND CCL3 RECOMBINATION REACTIONS

Canonical flexible transition state theory is applied to the recombina tion of CX3 radicals (X = H, F, CI) using a simple model for the poten tial-energy surface. The limiting high-pressure rate coefficient, k(in finity), is calculated, using Monte Carlo integration with stratified sampling for the three reactions in the temperature range from 300 to 2000 K. k(infinity) exhibits a negative temperature dependence, which becomes more pronounced as the size of X increases. There is a good ag reement between the present results and some of the available experime ntal data. The factors that influence the negative temperature depende nce of k(infinity) and the relative magnitude of k(infinity) for the t hree reactions are investigated.