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Theoretical studies of \({{\mathrm{{CN} + {H}}_{2}({\mathrm{D}}_{2})}}\) reactions: competition between H(D)-abstractions in \({\mathrm{H(D) + HCN(DCN)/HNC(DNC)}} \) channels

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Abstract

The \(\hbox {CN} + \hbox {H}_{2}\) reaction was investigated by considering the two possible channels, \(\hbox {H} + \hbox {HCN}\) and \(\hbox {H} + \hbox {HNC}\), taking into account the isotopic effects and with the vibrationally excited states. The frequencies and structures for all species of the \(\hbox {CN} + \hbox {H}_{2}/\hbox {D}_{2}\) reaction were calculated using G3 method for further kinetics calculation. The thermal rate constants were calculated using the conventional transition-state theory (TST) and canonical variational transition-state theory (CVT) by APUAMA code, over the temperature range from 200 to 4000 K. In addition, rate coefficients for vibrationally excited reactants CN (v = 1) or \(\hbox {H}_{2}\) (v = 1) or \(\hbox {D}_{2}\) (v = 1) are presented. The branching ratio for the partitioning into H/D + HCN/DCN or H/D + HNC/DNC has, also, been determined. The results showed that the \(\hbox {CN} (v=0) + \hbox {H}_{2} (v=0) \rightarrow \hbox {H} + \hbox {HCN} \) channel is dominant at all range of temperature, while \(\hbox {CN } (v=1) + \hbox {H}_{2} (v=0) \rightarrow \hbox {H} + \hbox {HNC}\) channel is dominant at T \(\ge \) 1900 K. The isotopic effects are the same behavior that \(\hbox {CN}(v=0,1) + \hbox {H}_{2}(v=0,1) \rightarrow \hbox {H} + \hbox {HCN/HNC}\) reactions. Reasonable agreement was found between the experimental results and the rate constants predicted by conventional transition-state theory, with tunneling correction, using the theoretical transition-state properties.

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Authors and Affiliations

  1. Instituto de Física, Universidade Brasília, CP04455, Brasília, DF, CEP 70919-970, Brazil

    Alessandra F. Albernaz

  2. Laboratório Associado de Plasma – LAP, Instituto Nacional de Pesquisas Espaciais - INPE, CP515, São José dos Campos, SP, CEP 12247-970, Brazil

    Patricia R. P. Barreto

Authors
  1. Alessandra F. Albernaz
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  2. Patricia R. P. Barreto
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Correspondence to Alessandra F. Albernaz.

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Albernaz, A.F., Barreto, P.R.P. Theoretical studies of \({{\mathrm{{CN} + {H}}_{2}({\mathrm{D}}_{2})}}\) reactions: competition between H(D)-abstractions in \({\mathrm{H(D) + HCN(DCN)/HNC(DNC)}} \) channels. Theor Chem Acc 138, 93 (2019). https://doi.org/10.1007/s00214-019-2479-1

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