Carbon nitride: Ab initio investigation of carbon-rich phases

We have examined the potential energy hypersurfaces for the carbon-rich phases of carbon nitride, CN and C₃N, and discovered low-energy structures different from those reported previously. Trends in the preferred local bonding environments have been analyzed as a function of nitrogen content. For each composition, several structures with similar energies were found, but they have very different equilibrium volumes; the structure produced during synthesis will strongly depend on the preparation conditions. When low densities are favored, conjugated planar-ring structures with sp² hybridized carbon are most likely to be formed. These structures are similar to those suggested as potential photocatalytic materials. At high pressures, the preferred structures contain three-coordinate nitrogen and sp³ hybridized carbon, including the β-InS structure, which we predict to be the thermodynamically preferred structure for CN under positive hydrostatic pressures. This structure has a moderately high bulk modulus with a lower formation energy than β-C₃N₄ and so should be more easily synthesized.