Dehydrogenation of N_2H_X (X = 2 - 4) by nitrogen atoms: Thermochemical and kinetics

摘要

Thermochemical and kinetics of sequential hydrogen abstraction reactions from hydrazine by nitrogen atoms were studied. The dehydrogenation was divided in three steps, N_2H_4 + N, N_2H_3 + N, and N_2H_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~(-20) cm~3 molecule~(-1) s~(-1) at 298 K.