Recoverability of N4 x− Anions to Ambient Pressure: A First-Principles Study of cyclo- and syn-Tetranitrogen Units

Bondarchuk, S. V. (2021) Recoverability of N4 x− Anions to Ambient Pressure: A First-Principles Study of cyclo- and syn-Tetranitrogen Units. Journal of Physical Chemistry. с. 7368-7377.

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Резюме

In this paper, we have analyzed the possibility of various neutral and anionic forms of both cyclic and acyclic N4 species to be recovered to ambient conditions using state-of-the-art computational techniques. Phonon dispersion and mechanical properties calculations as well as ab initio molecular dynamics simulations revealed that syntetranitrogen units are kinetically stable only in the form of N4 4 anion. Meanwhile, salts of cyclic N4 (c-N4, tetrazete) with alkali, alkaline earth metals, and aluminum appeared to be dramatically stable at ambient conditions for a wide range of oxidation states of c-N4 x from x = 13. Varying both metal and stoichiometry, one can obtain salts with a wide range of properties: band gap (1-5 eV), bulk modulus (36?196 GPa), enthalpy of formation (from 21 to 660 kJ mol?1 ), and so forth. Thus, crystal structure prediction and comprehensive characterization, which included bonding nature, stability criteria, spectral properties along with thermodynamic and energetic characteristics of c-N4 and its salts (Na2N8, Li2N4, MgN4, and AlN4) as well as calcium salt of syn-N4 4 (Ca2N4) are performed in this work. The obtained results significantly expand our understanding of the possible forms of nitrogen existence in nature, which, if synthesized, can find a number of interesting applications.

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