Dehydrogenation of N{sub 2}H{sub X} (X = 2 − 4) by nitrogen atoms: Thermochemical and kinetics

Thermochemical and kinetics of sequential hydrogen abstraction reactions from hydrazine by nitrogen atoms were studied. The dehydrogenation was divided in three steps, N{sub 2}H{sub 4} + N, N{sub 2}H{sub 3} + N, and N{sub 2}H{sub 2} + N. The thermal rate constants were calculated within the framework of canonical variational theory, with zero and small curvature multidimensional tunnelling corrections. The reaction paths were computed with the BB1K/aug-cc-pVTZ method and the thermochemical properties were improved with the CCSD(T)/CBS//BB1K/aug-cc-pVTZ approach. The first dehydrogenation step presents the lowest rate constants, equal to 1.22 × 10{sup −20} cm{sup 3} molecule{sup −1} s{sup −1} at 298 K.