GW quasiparticle bandgaps of anatase TiO2 starting from DFT+U

TL;DR

This study explores how starting from DFT+U calculations influences GW quasiparticle bandgap predictions for anatase TiO2, proposing an optimal Hubbard U value for more accurate results.

Contribution

It introduces a simple iterative method to determine the Hubbard U parameter that yields more accurate GW bandgap calculations for TiO2.

Findings

Optimal Hubbard U reduces the GW bandgap to 3.3 eV from 3.7 eV.

The method applies similarly to rutile TiO2.

Starting Hamiltonian significantly affects GW quasiparticle energies.

Abstract

We investigate the quasiparticle band structure of anatase TiO2, a wide gap semiconductor widely employed in photovoltaics and photocatalysis. We obtain GW quasiparticle energies starting from density-functional theory (DFT) calculations including Hubbard U corrections. Using a simple iterative procedure we determine the value of the Hubbard parameter yielding a vanishing quasiparticle correction to the fundamental band gap of anatase TiO2. The band gap (3.3 eV) calculated using this optimal Hubbard parameter is smaller than the value obtained by applying many-body perturbation theory to standard DFT eigenstates and eigenvalues (3.7 eV). We extend our analysis to the rutile polymorph of TiO2 and reach similar conclusions. Our work highlights the role of the starting non-interacting Hamiltonian in the calculation of GW quasiparticle energies in TiO2, and suggests an optimal Hubbard parameter for future calculations.