Diverse Chemistry of Stable Hydronitrogens, and Implications for Planetary and Materials Sciences

TL;DR

This study systematically explores the high-pressure stability and diversity of nitrogen hydrides, revealing new compounds and phases with unique properties, and discusses implications for planetary science and high-energy materials.

Contribution

It reports the discovery of previously unknown N-H compounds and phases stabilized at high pressures up to 800 GPa, expanding understanding of high-pressure nitrogen chemistry.

Findings

High-pressure stabilizes new N-H compounds with unique structures.

NH3 becomes unstable above ~460 GPa.

High-pressure N-H chemistry is more diverse than organic chemistry.

Abstract

Nitrogen hydrides, including ammonia (NH3), hydrazine (N2H4), hydrazoic acid (HN3) and etc, are compounds of great fundamental and applied importance. Their high-pressure behavior is important because of their abundance in giant planets and because of the hopes of discoverying high-energy-density materials. Here, we have performed a systematic investi- gation on the structural stability of N-H system in a pressure range up to 800 GPa through evolutionary structure prediction simulations. Surprisingly, we found that high pressure stabilizes a series of previously unreported compounds with peculiar structural and electronic properties, such as the N4H, N3H, N2H and NH phases composed of nitrogen backbones, the N9H4 phase containing two dimensional metallic nitrogen planes and novel N8H, NH2, N3H7, NH4 and NH5 molecular phases. Another surprise is that NH3 becomes thermodynamically unstable above ~460 GPa. We found that high-pressure chemistry is much more diverse that hydrocarbon chemistry at normal conditions, leading to expectations that N-H-O and N-H-O-S systems under pressure are likely to possess richer chemistry than the known organic chemistry. This, in turn, opens a possibility of nitrogen-based life at high pressure. The predicted phase diagram of the N-H system also provides a reference for synthesis of high-energy-density materials.