Unexpected Robustness of the Band Gaps of TiO2 under High Pressures

Abstract: Titanium dioxide (TiO2) is a wide band gap semiconducting material which is promising for photocatalysis. Here we present first-principles calculations to study the pressure dependence of structural and electronic properties of two TiO2 phases: the cotunnite-type and the Fe2P-type structure. The band gaps are calculated using density functional theory (DFT) with the generalized gradient approximation (GGA), as well as the many-body perturbation theory with the GW approximation. The band gaps of both phases are found to be unexpectedly robust across a broad range pressures. The corresponding pressure coefficients are significantly smaller than that of diamond and silicon carbide (SiC), whose pressure coefficient is the smallest value ever measured by experiment. The robustness originates from the synchronous change of valence band maximum (VBM) and conduction band minimum (CBM) with nearly identical rates of changes. A step-like jump of band gaps around the phase transition pressure point is expected and understood in light of the difference in crystal structures.