Abstract
The reaction CH(X{sup 2}{Pi}) + H{sub 2} was studied as a function of temperature in the range 200-400 K at 4 Torr total pressure and as a function of total pressure in the range 2-592 Torr at 298 K. CH radicals were generated by excimer laser photolysis of CHClBr{sub 2}/Ar mixtures and were detected by laser-induced fluorescence. The reaction proceeds along two pathways: Above 300 K, production of CH{sub 2} + H dominates with an activation energy of 13.82 {plus minus} 4.19 kJ{center dot}mol{sup {minus}1}, whereas below 300 K, the rate constants exhibit a negative temperature dependence with an activation energy of -6.12 {plus minus} 1.93 kJ{center dot}mol{sup {minus}1} consistent with an adduct formation followed by collisional stabilization. The limiting rate constants k{sub 0} and k{sub {infinity}} and the broadening factor F{sub c} were determined from the pressure dependence. A transition-state-theory model was applied to analyze the experimental results.
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