Theoretical investigation of N (²D) + HOX (Cl, Br) reaction

ABSTRACT

The doublet potential-energy surface for the reaction, N (²D) + HOX (X = Cl, Br) has been studied employing both second-order Møller-Plesset and density-functional theory. The energies of the involved species have been refined using the complete basis set and coupled-cluster singles and double (triples) methods. Angular momentum-resolved (i.e. J-resolved) microcanonical variational transition state theory rate constant calculations are carried out to gain insight into the dynamics of this reaction. The minimum energy path of the title reaction occurs predominantly via the insertion-dissociation mechanism. The energetically most favourable product channels lead to the formation of HNO + X and NO + HX. The results indicate that the reaction shows positive temperature dependence in the temperature range of 200–500 K.

GRAPHICAL ABSTRACT

KEYWORDS:

• Density-functional theory
• microcanonical variational transition state theory
• rate constant
• dynamics

Acknowledgements

J.P. is thankful to Indian Institute of Technology Patna for financial support and for providing research facilities at IIT Patna.

Disclosure statement

No potential conflict of interest was reported by the authors.

ORCID

Ranga Subramanian http://orcid.org/0000-0002-4989-7416

Additional information

Funding

This work was supported by Indian Institute of Technology Patna [grant number IITP].