• Sisir K Sarkar

      Articles written in Journal of Chemical Sciences

    • Infrared diode laser probing of methane in excimer laser photolysis of pyruvic acid

      Sisir K Sarkar Jai P Mittal George W Flynn

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      The photodissociation of pyruvic acid at 193 nm has been studied and one of the photoproducts, methane, was detected using an infrared diode laser absorption probe technique. Using second-derivative absorption spectroscopy at 1346.326 cm-1[R(-)(7) transition in v4 band], the progress of the reaction was monitored. The quantum yield of formation of methane = 0.09 ± 0.01 and was further corroborated by a simple measurement of pressure changes following the photolysis. The secondary photolysis of the photoproduct acetaldehyde via the established route was found to be negligible. This result may help to account for the energetics of the photodissociation process by a 6.4 eV excimer laser photon. The possibility of using this technique to examine the nascent methane molecule in real-time domain to gain better insight of the dissociation dynamics is also indicated.

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

      Rajesh K Vatsa Sisir K Sarkar Jai P Mittal

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      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.

    • Modelling of multifrequency IRMPD for laser isotope separation

      Akshaya K Nayak Sisir K Sarkar

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      The process of infrared multiple photon dissociation (IRMPD) of molecules is of great fundamental importance and has practical significance, such as isotope separation etc. Unfortunately, a clear insight into the process has been hindered by the bewildering array of important variables affecting MPD. The dissociation probability γ (φ) i.e. the yield has been found to be a sensitive function of laser fluence φ along with numerous other parameters like laser frequency, gas pressure etc. We have shown that in single frequency IRMPD, an accurate quantitative characterization of the dissociation probability can be adequately expressed by a ‘power law’ model with two fitting parameters namely critical fluence, φc and multiphoton order,m. This model was exploited in analysing our MPD results on various systems. However, the small isotope shift encountered in heavy elements and the sticking phenomenon observed in small light molecules restrict respectively the separation factor and the dissociation yield. These problems can effectively be tackled by irradiation with multifrequency laser beams which can be chosen appropriately on the basis of spectroscopic features. Based on our success in single frequency model, multifrequency IRMPD is modelled by a functional form containing the product of power law terms for individual fluences on irradiation frequencies. This model is successfully benchmarked with our experimental results on multifrequency LIS of tritium. Such knowledge can be utilized for appropriate separation process design, evaluation and optimization.

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