First-principles Hubbard U and Hund's J corrected approximate density-functional theory predicts an accurate fundamental gap in rutile and anatase TiO2

Abstract

Titanium dioxide (TiO$_2$) presents a long-standing challenge for approximate Kohn-Sham density-functional theory (KS-DFT), as well as to its Hubbard-corrected extension, DFT+$U$. We find that a previously proposed extension of first-principles DFT+$U$ to incorporate a Hund's $J$ correction, termed DFT+$U$+$J$, in combination with parameters calculated using a recently proposed linear-response theory, predicts fundamental band-gaps accurate to well within the experimental uncertainty in rutile and anatase TiO$_2$. Our approach builds upon established findings that Hubbard correction to both titanium $3d$ and oxygen $2p$ subspaces in TiO$_2$, symbolically giving DFT+$U^{d,p}$, is necessary to achieve acceptable band-gaps using DFT+$U$. This requirement remains when the first-principles Hund's $J$ is included. We also find that the calculated gap depends on the correlated subspace definition even when using subspace-specific first-principles $U$ and $J$ parameters. Using the simplest reasonable correlated subspace definition and underlying functional, the local density approximation, we show that high accuracy results from using a relatively uncomplicated form of the DFT+$U$+$J$ functional. For closed-shell systems such as TiO$_2$, we describe how various DFT+$U$+$J$ functionals reduce to DFT+$U$ with suitably modified parameters, so that reliable band gaps can be calculated for rutile and anatase with no modifications to a conventional DFT+$U$ code.