Pressure-stabilized Planar N4-ring and Bonding Properties in Manganese Nitrides

TL;DR

This study uses ab initio calculations to explore Mn-N compounds under high pressure, discovering a novel N-rich MnN4 phase with a planar N4 ring that could be a hard superconductor.

Contribution

First theoretical prediction of N-rich MnN4 with a planar N4 ring structure stabilized at high pressure.

Findings

Discovered N-rich MnN4 with a planar N4 ring at 40-100 GPa.

Identified phase transition sequence in Mn-N compounds under pressure.

Revealed covalent interactions influence hardness in N-rich Mn-N structures.

Abstract

Manganese nitrides should be with amazing properties and promised application, because manganese atom is particular for its magnetism, valence states, high electron density, etc., and N atoms in compounds form different substructures. It is hard to good synthesize manganese nitride crystals with all established means, therefore, theoretical studies are highly welcome. In this study, we systematically examined the stoichiometric phases spaces of Mn-N compounds from 0 to 100 GPa based on ab initio calculations, and constructed the high pressure magnetic phase diagram. Remarkably, N-rich MnN4 with a planar N4 ring was discovered for the first time in the pressure range from 40 to 100 GPa. The electronic structures reveal that the N4 ring is driven by the sp2 hybridization of nitrogen atoms. This phase with Tc=1.6 K and high bulk modulus B =381 GPa, which make it potentially interesting as a hard superconductive material. Moreover, the phase transition sequence for the MnN compound is summarized renewedly, the semi-conducting NM-zb phase (5 GPa) first transforms to metallic AFM-NiAs (40 GPa), which further transforms to the more stable metallic FM-rs phase. The mechanical properties show that covalent interaction has a great effect on N-rich structures' hardness and hardly effect on Mn-rich structures in Mn-N compounds.