Hydrogen atom abstraction from Piperazine by hydroxyl radical: a theoretical investigation

Dual level of quantum mechanical calculations have been carried out for hydrogen abstraction from Piperazine [HN(CH2CH2)(2)NH] initiated by OH radical. Geometry optimisation and frequency calculations of all species involved in the titled reaction have been performed at M06-2X/6-31+ G(d,p) level of theory. For the accuracy in the thermochemistry and kinetics data, single-point energy calculations have been further carried out at coupled cluster CCSD(T) method along with 6-311G(d, p) basis set. An energy profile diagram for the reaction has been plotted along with pre-reactive and post-reactive complexes at entrance and exit channels. Intrinsic reaction coordinates (IRCs) calculations have been performed for identification of real transition states that connect it via reactant to product. Our result shows that the H-atom abstraction takes place from the C-H position of Piperazine. The rate constant is calculated using canonical transition state theory (CTST) is found to be 2.86 x 10(-10) cm(3) molecule(-1) s(-1) which is in good agreement with the reported experimental rate constant (2.38 +/- 0.28) x 10(-10) cm(3) molecule(-1) s(-1) at 298 K. We have also reported rate constant for the temperature range 300-500 K. Using group-balance isodesmic reaction, the standard enthalpies of formation for Piperazine and product radicals generated by hydrogen abstraction are reported. The branching ratios for both reaction channel (i.e. H-abstraction from -CH2 and -NH position of Piperazine) are found to be 93% and 7%, respectively. The calculated atmospheric life time of Piperazine is found to be 0.97 hour. [GRAPHICS] .