We provide a comprehensive account of structural, electronic, and optical properties of carbon-nitride (C3N4) polymorphs. We employ density-functional theory with two different basis sets for better predictions of structural and electronic band-gap properties: (a) a localized tight-binding basis with an improved semi-empirical exchange functional for more rapid and robust predictions; and (b) a plane-wave basis using a hybrid functional for validation. The predicted lattice constants, bulk moduli, and band gaps are in good agreement with existing experiments and theory, which verifies our predictions are reliable and basis-set independent. The optimal band gap, HOMO-LUMO position, and optical properties show the suitability of γ-C3N4~ in photocatalytic applications, while its work function shows orientation dependence with favorable valence and conduction band edges along the (110) direction. We also explore the effect of pressure on structural-stability, optical properties and photocatalytic behavior of γ-C3N4. Our study suggest the opportunity to tune these properties by introducing defects to further improve photocatalytic performance of nitrides.
Available at: http://works.bepress.com/duane_johnson/143/