Origin of the Nonmonotonic Pressure Dependence of the Band Gap in the Orthorhombic Perovskite CsPbBr3

The perovskite CsPbBr3 exhibits an unusual nonmonotonic dependence of the band gap on increasing pressure to about 2.0 GPa as compared to conventional semiconductors. Using the first-principles calculation method, we show that under pressure, isotropic volume deformation induces considerable compression of the Pb–Br bond length and thus an enhanced interaction between atomic orbitals of the antibonding valence band maximum states and the mostly nonbonding conduction band minimum states, resulting in a monotonic decrease in the band gap. On the other hand, structural relaxation tends to reduce the strain energy by decompressing the Pb–Br bond length and simultaneously compressing the Pb–Br–Pb bond angle, which increases the band gap energy. We find that the competition between the volume deformation effect and structural relaxation effect is the origin of the nonmonotonic behavior of the dependence of the band gap on pressure.