First-principles calculations on solid nitrogen: A comparative study of high-pressure phases
Abstract
There is experimental evidence that nitrogen forms a polymeric solid under pressure. In this study, we compare various solid nitrogen phases by means of ab initio calculations based on density-functional theory to describe solid nitrogen at different pressures. We show that two phases with covalent bonds in all three dimensions are energetically the most favored at pressures of 50 200GPa and that the layered black phosphorus phase becomes lower in enthalpy at pressures exceeding 200GPa , at least at low temperatures. However, according to our results, black phosphorus is unstable at pressures close to 200GPa . We further present band structure and density of states calculations for the relevant known phases at several pressures and show that black phosphorus is metallic when metastable, whereas the lower-pressure phases remain dielectric with pressure-dependent band gaps. Also the questionable experimental relevance of several of the previously proposed structures is addressed.
- Publication:
-
Physical Review B
- Pub Date:
- April 2008
- DOI:
- 10.1103/PhysRevB.77.144109
- Bibcode:
- 2008PhRvB..77n4109K
- Keywords:
-
- 71.15.Mb;
- 81.40.Vw;
- 71.20.Mq;
- Density functional theory local density approximation gradient and other corrections;
- Pressure treatment;
- Elemental semiconductors