Abstract
The band structures of cubic O and monoclinic CuO crystals have been calculated by means of the first-principles orthogonalized linear combination of atomic orbitals method. Using the wave functions obtained, the frequency-dependent interband optical conductivities are also evaluated. The results show O to be a direct-gap semiconductor, while CuO is semiconductorlike with an intrinsic hole population at the top of the valence band (VB). By comparing with a variety of existing data, we conclude that band theory works extremely well for O, but is less satisfactory for CuO. This could be due to strong correlation effects for states near the top of the VB in CuO. A careful reanalysis of optical data and excitonic spectra in O in conjunction with our calculations suggests a complete reinterpretation of these data. A clear distinction between the intrinsic gap and the optical gap is argued. We conclude that the intrinsic gap in O is of the order of 0.8 eV, while the optical gap is of the order 2.0–2.3 eV. The excitonic series in O is due to the Coulombic attraction of the hole at the top of the VB and the electron in the next-higher conduction band (CB), not the lowest CB, because of the forbidden symmetry associated with angular-momentum conservation. This reinterpretation of the excitonic data is also consistent with a calculated low value for the static dielectric constant of order of 4 for O.
- Received 7 March 1989
DOI:https://doi.org/10.1103/PhysRevB.40.7684
©1989 American Physical Society