Nand Kishor Gour
Articles written in Journal of Chemical Sciences
Volume 126 Issue 6 November 2014 pp 1789-1801 Regular Articles
Theoretical investigation has been carried out on the kinetics and reaction mechanism of the gas-phase reaction of 3-hydroxy-2-butanone (3H2B) with OH radical using dual-level procedure employing the optimization at DFT(BHandHLYP)/6-311++G(d,p) followed by a single-point energy calculation at the CCSD(T)/6-311++G(d,p) level of theory. The pre- and post reactive complexes are also validated at entrance and exit channels, respectively. Thus reaction may be proceed via indirect mechanism. The intrinsic reaction coordinate (IRC) calculation has also been performed to confirm the smooth transition from a reactant to product through the respective transition states. The rate coefficients were calculated for the first time over a wide range of temperature (250-450 K) and described by the following expression: kOH = 7.56 × 10−11exp[−(549.3 ± 11.2)/T] cm3 molecule-1s-1. At 298 K, our calculated rate coefficient 1.20 × 10−11 cm3 molecule-1 s-1 is in good agreementwith the experimental results. Our calculation indicates that H-abstraction from 𝛼-C-H site of 3H2B is the dominant reaction channel. Using group-balanced isodesmic reactions, the standard enthalpies of formation for 3H2B and radicals generated by hydrogen abstraction are reported for the first time. The branching ratios of the different reaction channels are also determined. Also, the atmospheric lifetime of 3H2B is also calculated to be 1.04 days.
Volume 127 Issue 6 June 2015 pp 1015-1023 Regular Articles
A theoretical investigation has been carried out on the mechanism, kinetics, and thermochemistry of gas-phase reaction of 2,2,2-trifluoroethyl butyrate (TFEB, CH3CH2CH2C(O)OCH2CF3) with OH radicals using a modern DFT functional. The involvement of pre- and post-reactive complexes was explored and the reaction profiles were modeled. Energetic calculations were performed using the M06-2X/6-31+G(d,p) method. The intrinsic reaction coordinate (IRC) calculation has been performed to confirm the smooth transition from the reactant to product through the respective transition state. It has been found that the dominant path of the H-atom abstraction takes place from the –CH2- position, which is attached with the methyl group at the one end of TFEB. Theoretically calculated rate constant at 298 K using canonical transition state theory (CTST) is found to be in reasonable agreement with the experimental data. Using group-balanced isodesmic procedure, the standard enthalpy of formation for TFEB is reported for the first time. The branching ratios of the different reaction channels are also determined. The atmospheric lifetime of TFEB is determined to be 6.8 days.
Volume 134, 2022
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