Exploring novel phases of Cd–O system at ambient pressure

Abstract

First-principles evolutionary searches are used to explore stable Cd–O compounds at ambient pressure. Besides the well-known rock-salt CdO, a new cubic thermodynamically stable phase CdO2 with space group Pa3 and two metastable compounds: zinc-blende and wurtzite phases of CdO have been discovered at ambient pressure. Among these, CdO2 was successfully synthesized with perfect structural agreement to our theoretical predictions. The global stability of the well known rock-salt phase of CdO, our calculations of elastic constants and phonon dispersion curves demonstrate that the Pa3, zinc-blende and wurtzite structures are mechanically and dynamically stable. Finally, the state-of-the-art LDA-1/2 methods reveal that at ambient conditions, zinc-blende and wurtzite phases are semiconducting with a direct band gap (Γ–Γ) of 0.89 eV and 0.97 eV respectively; whereas the semiconducting cubic-Pa3 structure shows direct band gap (Γ–Γ) of ∼2.93 eV and an indirect band gap of ∼2.58 eV agreeing well with the experimental value of ∼2.4 eV.