Journal of Chemical Theory and Computation
Journal of Chemical Theory and Computation
5 years ago

Performance of the G0W0 Method in Predicting the Electronic Gap of TiO2 Nanoparticles

Performance of the G0W0 Method in Predicting the Electronic Gap of TiO2 Nanoparticles
Ángel Morales-García, Rosendo Valero, Francesc Illas
Using a relativistic all-electron description and numerical atomic-centered orbital basis set, the performance of the G0W0 method on the electronic band gap of (TiO2)n nanoparticles (n = 1–20) is investigated. Results are presented for G0W0 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 G0W0 method, which are consistent with the variational ΔSCF 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 ΔSCF 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 ΔSCF and G0W0 methods. (ii) The G0W0 approach can be successfully used to study the electronic band gap of realistic size nanoparticles at an affordable computational cost with a ΔSCF 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 G0W0 approach emerges as an accurate method to investigate the photocatalytic properties of both nanoparticles and extended semiconductors.

Publisher URL: http://dx.doi.org/10.1021/acs.jctc.7b00308

DOI: 10.1021/acs.jctc.7b00308

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