Dissociation of nitromethane has been observed when a mixture of CF₂HCl and CH₃NO₂ is irradiated using pulsed TEA CO₂ laser at 9R (24) line (1081 cm^-1), which is strongly absorbed by CF₂HCl but not by CH₃NO₂. Under low laser fluence conditions, only nitromethane dissociates, whereas at high fluence CF₂HCl also undergoes dissociation, showing that dissociation occurs via the vibrational energy transfer processes from the TEA CO₂ laser-excited CF₂HCl to CH₃NO₂. Time-resolved infrared fluorescence from vibrationally excited CF₂HCl and CH₃NO₂ molecules as well as UV absorption of CF₂ radicals are carried out to elucidate the dynamics of excitation/dissociation and the chemical reactions of the dissociation products.

The dynamics of formation of oxygen atoms after UV photoexcitation of SO₂ in the gas-phase was studied by pulsed laser photolysis-laser-inducedfluorescence ‘pump-and-probe’ technique in a flow reactor. SO₂ at room-temperature was excited at the KrCl excimer laser wavelength (222.4 nm) and O(³P_j) photofragments were detected under collision-free conditions by vacuum ultraviolet laser-induced fluorescence. The use of narrow-band probe laser radiation, generated viaresonant third-order sum-difference frequency conversion of dye laser radiation in Krypton, allowed the measurement of the nascent O(³P_j=2,1,0) fine-structure state distribution:n_j=2/n_j=1/n_j=0 = (0.88 ± 0.02)/(0.10 ± 0.01)/(0.02 ± 0.01). Employing NO₂photolysis as a reference, a value of Φ₀(³P) = 0.13 ± 0.05 for the absolute O(³P) atom quantum yield was determined. The measured O(³P) quantum yield is compared with the results of earlier fluorescence quantum yield measurements. A suitable mechanism is suggested in which the dissociation proceeds via internal conversion from high rotational states of the initially excited SO₂(~C¹B₂ (1, 2, 2) vibronic level to nearby continuum states of the electronic ground state.

The collision-free, room temperature gas-phase photodissociation dynamics of CH₃CFCl₂ (HCFC-141b) was studied using Lyman-𝛼 laser radiation (121.6 nm) by the laser photolysis/laserinduced fluorescence `pump/probe’ technique. Lyman-𝛼 radiation was used both to photodissociate the parent molecule and to detect the nascent H atom products via ($2p^2$P → $1s^2$S) laser-induced fluorescence. Absolute H atom quantum yield, $\phi_H = (0.39 \pm 0.09)$ was determined by calibration method in which CH₄ photolysis at 121.6 nm was used as a reference source of well-defined H atom concentrations. The line shapes of the measured H atom Doppler profiles indicate a Gaussian velocity distribution suggesting the presence of indirect H atom formation pathways in the Lyman-𝛼 photodissociation of CH₃CFCl₂. The average kinetic energy of H atoms calculated from Doppler profiles was found to be $E_{\text{T(lab)}} = (50 \pm 3)$ kJ/mol. The nearly statistical translational energy together with the observed Maxwell-Boltzmann velocity distribution indicates that for CH₃CFCl₂ the H atom forming dissociation process comes closer to the statistical limit.