Pentazole and Ammonium Pentazolate: Crystalline Hydro-Nitrogens at High Pressure

TL;DR

This paper predicts two new high-pressure crystalline compounds, pentazole and ammonium pentazolate, using first principles calculations, and provides their stability ranges and spectroscopic signatures for experimental identification.

Contribution

The study introduces the first theoretical prediction of pentazole and ammonium pentazolate crystals stable at high pressures, expanding the understanding of nitrogen-rich hydro-nitrogen compounds.

Findings

Pentazole (N5H) stable above 50 GPa.

Ammonium pentazolate ((NH4)(N5)) stable above 30 GPa.

Transformation of ammonium azide to ammonium pentazolate above 12.5 GPa.

Abstract

Two new crystalline compounds, pentazole (N_{5}H) and ammonium pentazolate (NH_{4})(N_{5}), both featuring cyclo-{\rm N_{5}^{-}} are discovered using first principles evolutionary search of the nitrogen-rich portion of the hydro-nitrogen binary phase diagram (N_{x}H_{y}, x\geqy) at high pressures. Both crystals consist of the pentazolate N_{5}^{-} anion and ammonium NH_{4}^{+} or hydrogen H^{+} cations. These two crystals are predicted to be thermodynamically stable at pressures above 30 GPa for (NH_{4})(N_{5}) and 50 GPa for pentazole N_{5}H. The chemical transformation of ammonium azide (NH_{4})(N_{3}) mixed with di-nitrogen (N_{2}) to ammonium pentazolate (NH_{4})(N_{5}) is predicted to become energetically favorable above 12.5 GPa. To assist in identification of newly synthesized compounds in future experiments, the Raman spectra of both crystals are calculated and mode assignments are made as a function of pressure up to 75 GPa.