• Rajesh K Vatsa

Articles written in Journal of Chemical Sciences

• TEA CO2 laser-induced reaction of CH3NO2 with CF2HCl: A mechanistic study

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.

• Absolute quantum yield measurements for the formation of oxygen atoms after UV laser excitation of SO2 at 222-4 nm

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(3Pj) 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(3Pj=2,1,0) fine-structure state distribution:nj=2/nj=1/nj=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.

• Lyman-𝛼 photodissociation of CH3CFCl2 (HCFC-141b): Quantum yield and translational energy of hydrogen atoms

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.

• # Journal of Chemical Sciences

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Volume 131 | Issue 7
July 2019

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