The multiphoton absorption and decomposition of CDC13 induced by TEA-C02 laser pulses have been studied at low pressures of CDC13 (0.3 Torr) and with the addition of CHC13 and Ar as bath gases. The laser absorption cross section was also measured as a function of incident fluence in the range 0.01-0.7 J/cm1 2. The reaction probability per pulse was measured at fluences of 7-60 J/cm2 as was the effect of added CHC13 and Ar at 20 and 33 J/cm2. The experimental results were modeled with a master equation with explicit consideration of rotational and anharmonic bottlenecks. The calculations in the high-pressure region allowed obtainment of information about the energy transferred by collision of the vibrationally excited CDC13 with CHC13 and Ar. An energy-dependent value of

The rate constant of the reaction between CCl2 radicals and HCl was experimentally determined. The CCl2 radicals were obtained by infrared multiphoton dissociation of CDCl3. The time dependence of the CCl2 radicals' concentration in the presence of HCl was determined by laser‐induced fluorescence. The experimental conditions allowed us to associate the decrease in the concentration of radicals to the self‐recombination reaction to form C2Cl4 and to the reaction with HCl to form CHCl3. The rate constant for the self‐recombination reaction was determined to be in the high‐pressure regime. The value obtained at 300 K was (5.7 ± 0.1) × 10−13 cm3 molecule−1 s−1, whereas the value of the rate constant measured for the reaction with HCl was (2.7 ± 0.1) × 10−14 cm3 molecule−1 s−1.

An experimental setup that coupled IR multiple‐photon dissociation (IRMPD) and laser‐induced fluorescence (LIF) techniques was implemented to study the kinetics of the recombination reaction of dichlorocarbene radicals, CCl2, in an Ar bath. The CCl2 radicals were generated by IRMPD of CDCl3. The time dependence of the CCl2 radicals’ concentration in the presence of Ar was determined by LIF. The experimental conditions achieved allowed us to associate the decrease in the concentration of radicals to the self‐recombination reaction to form C2Cl4. The rate constant for this reaction was determined in both the falloff and the high‐pressure regimes at room temperature. The values obtained were k0 = (2.23 ± 0.89) × 10−29 cm6 molecules−2 s−1 and k∞ = (6.73 ± 0.23) × 10−13 cm3 molecules−1 s−1, respectively.

We have studied the association reaction of the CF(2)Cl radicals with O(2) in presence of N(2). The infrared multiple photon dissociation (IRMPD) technique with a homemade TEA CO(2) laser was used for the CF(2)Cl radical generation and the vibrational chemiluminiscence technique was set up for the study of the reaction kinetics. The time-resolved IR fluorescence of the vibrationally excited CF(2)O photoproduct was used to measure the disappearance rate of these radicals. A kinetic mechanism is presented to account for the rate of production of CF(2)O(*). The CF(2)Cl radical association reaction rate with O(2), evidence of a direct channel of photoproduct formation and its reaction rate, and the CF(2)O(*) collisional deactivation rate have been obtained.