Relative energies and electronic structures of CoO polymorphs through ab initio diffusion quantum Monte Carlo

Abstract

We present a many-body diffusion quantum Monte Carlo (DMC) study on the ground- and excited state properties of crystalline CoO polymorphs. To our knowledge, DMC is the only electronic structure method available to provide correct energetic ordering within experimental error bars between the three CoO polymorphs: rocksalt, wurtzite, and zinc blende. We compare these results to density functional theory (DFT) using state-of-the-art functionals such as SCAN. For the structural properties, such as the lattice parameters and bulk moduli, our results are comparable to HSE and SCAN. Using DMC, we calculated the indirect and direct optical gaps as 3.8(2) and 5.2(2) eV. Our indirect optical gap compares well with the conductivity measurements of 3.6(5) eV and $GW$ calculations with 3.4 eV. Similarly, we obtained the DMC indirect and direct quasiparticle gaps as 3.9(2) and 5.5(2) eV. DMC direct quasiparticle gaps compare well with the direct band gap of 5.53 eV obtained from ellipsometry studies.