Absolute and Relative-Rate Kinetics Experiments and Direct Dynamics Computations for the Reaction of Br Atoms with CH2ClBr

Abstract

Kinetics of the reaction Br + CH2ClBr <--> CHClBr + HBr (1, -1) were studied experimentally in the forward direction. The absolute reaction kinetics method of laser flash photolysis coupled with Br atom resonance fluorescence detection and three different relative-rate methods with gas-chromatographic analysis were applied to carry out the experiments. The rate constants determined were found to obey the Arrhenius law in the wide temperature range of T = 293-785 K providing the kinetic expression k1 = (2.8 +/- 0.1) x 10(13) exp[-(47.6 +/- 0.3) kJ mol(-1)/RT] cm3 mol(-1) s(-1) (the errors given refer to 1sigma precision). An ab initio direct dynamics method was used to study reaction (1, -1) theoretically. The electronic structure information including geometries, gradients, and force constants was obtained at the MP2 level of theory; and energies were improved at higher theoretical levels. Rate constants were calculated using the canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200-1000 K. Theory substantially underestimates k1 compared to experiment. The agreement was found good with k(-1) reported previously predicting positive temperature dependence. The experimental kinetic parameters were utilized in thermochemical calculations yielding the recommended standard enthalpy of formation of delta(f)H degrees (298) (CHClBr) = (140 +/- 4) kJ mol(-1) (with 2sigma accuracy given).