Performance of the G(0)W(0) method in predicting the electronic gap of TiO2 nanoparticles

Abstract

Using a relativistic all-electron description and numerical atomic-centered orbital basis set, the performance of the G(0)W(0) method on the electronic band gap of (TiO2) nanoparticles (n = 1-20) is investigated. Results are presented for G(0)W(0) on top of hybrid (PBE0 and a modified version with 12.5% of Fock exchange) functionals. The underestimation of the electronic band gap from Kohn-Sham orbital energies is corrected by the quasiparticle energies from the G(0)W(0) method, which are consistent with the variational Delta SCF approach. A clear correlation between both methods exists regardless of the hybrid functional employed. In addition, the vertical ionization potential and electron affinity from quasiparticle energies show a systematic correlation with the Delta SCF calculated values. On the other hand, the shape of the nanoparticles promotes some deviations on the electronic band gap. In conclusion, this study shows the following: (i) A systematic correlation exists between band gaps, ionization potentials, and electron affinities of TiO2 nanoparticles as predicted from variational Delta SCF and G(0)W(0) methods. (ii) The G(0)W(0) approach can be successfully used to study the electronic band gap of realistic size nanoparticles at an affordable computational cost with a Delta SCF accuracy giving results that are directly related with those from photoemission spectroscopy. (iii) The quasiparticle energies are explicitly required to shed light on the photocatalytic properties of TiO2. (iv) The G(0)W(0) approach emerges as an accurate method to investigate the photocatalytic properties of both nanoparticles and extended semiconductors.