Quasiparticle and Optical Properties of Rutile and Anatase TiO2_{2}

Quasiparticle excitation energies and optical properties of TiO$_{2}$ in the rutile and anatase structures are calculated using many-body perturbation theory methods. Calculations are performed for a frozen crystal lattice; electron-phonon coupling is not explicitly considered. In the GW method, several approximations are compared and it is found that inclusion of the full frequency dependence as well as explicit treatment of the Ti semicore states are essential for accurate calculation of the quasiparticle energy band gap. The calculated quasiparticle energies are in good agreement with available photoemission and inverse photoemission experiments. The results of the GW calculations, together with the calculated static screened Coulomb interaction, are utilized in the Bethe-Salpeter equation to calculate the dielectric function $\epsilon_{2}(\omega)$ for both the rutile and anatase structures. The results are in good agreement with experimental observations, particularly the onset of the main absorption features around 4 eV. For comparison to low temperature optical absorption measurements that resolve individual excitonic transitions in rutile, the low-lying discrete excitonic energy levels are calculated with electronic screening only. The lowest energy exciton found in the energy gap of rutile has a binding energy of 0.13 eV. In agreement with experiment, it is not dipole allowed, but the calculated exciton energy exceeds that measured in absorption experiments by about 0.22 eV and the scale of the exciton binding energy is also too large. The quasiparticle energy alignment of rutile is calculated for non-polar (110) surfaces. In the GW approximation, the valence band maximum is 7.8 eV below the vacuum level, showing a small shift from density functional theory results.Comment: Submitted to Physical Review

The GW space-time method for the self-energy of large systems

We present a detailed account of the GW space-time method. The method increases the size of systems whose electronic structure can be studied with a computational implementation of Hedin's GW approximation. At the heart of the method is a representation of the Green function G and the screened Coulomb interaction W in the real-space and imaginary-time domain, which allows a more efficient computation of the self-energy approximation Sigma = iGW. For intermediate steps we freely change between representations in real and reciprocal space on the one hand, and imaginary time and imaginary energy on the other, using fast Fourier transforms. The power of the method is demonstrated using the example of Si with artificially increased unit cell sizes. (C) 1999 Elsevier Science B.V