Cycloaddition of molecular dinitrogens: formation of tetrazete anion (N₄^-; D_2h) through associative electron attachment

Abstract

State-specific reaction dynamics induced through the resonant attachment of a low energy electron (LEE) offers hitherto unavailable opportunities for the chemical synthesis of theoretically possible chemical structures. Using ab initio quantum chemical methods, this possibility is illustrated for the cycloaddition reaction of dinitrogen molecules to produce the anion of tetrazete $N_4^{-}$, which is an all-nitrogen cyclic molecule. This LEE induced cycloaddition reaction, which is an associative electron attachment reaction, is initiated by the resonant attachment of a near 12 eV LEE to the dimer of non-interacting molecular dinitrogens, (N${}_2$)${}_2$. The resulting 2p1h state of the (N${}_2$)${}_2$ undergoes a barrierless cycloaddition reaction and produce N${}_4^{-}$. In this reaction, the kinetic energy of the LEE is stored in the geometrical metastable structure of $N_4^{-}$ and make this process a potential method for storing energy.

GRAPHICAL ABSTRACT

Keywords:

• Electronic resonances
• cycloaddition
• tetrazete
• metastable anion
• Feshbach resonances

Acknowledgements

The author is grateful for discussions with Prof. E. Krishnakumar and Prof. Vaibhav Prabhudesai. The author thank the reviewer for the valuable comments that improved the manuscript. This paper is dedicated to Prof. N. Moiseyev on his 70th birthday.

Disclosure statement

No potential conflict of interest was reported by the authors.