Implementation and application of a DFT$+U$$+V$ approach within the all-electron FLAPW method

TL;DR

This paper implements a DFT+U+V approach within the all-electron FLAPW method, enabling more accurate modeling of correlated materials by including intersite Coulomb interactions and deriving parameters from first principles.

Contribution

It introduces a novel implementation of DFT+U+V in the FLAPW method with first-principles parameter calculation, improving the description of correlated materials.

Findings

Enhanced accuracy in modeling covalent, semiconducting, and charge-transfer materials.

Demonstrated the importance of the V term for intersite interactions.

Validated results against experiments and GW calculations.

Abstract

We present an implementation of the density-functional theory DFT$+U$$+V$ formalism within the all-electron full-potential linearized augmented-plane-wave (FLAPW) method as implemented in the FLEUR code. The DFT$+U$$+V$ formalism extends DFT, supplemented by the onsite Coulomb interaction $U$, to address local correlation effects in localized states by incorporating intersite Coulomb interaction terms $V$. It holds promise for improving charge and bond disproportionation, charge and orbital ordering, charge density wave formation, charge transfer, and the intersite correlation resulting from hybridization between states of neighboring sites in a solid. $U$ and $V$ parameters are obtained from first principles using the constrained random-phase approximation (cRPA) employing two different atom basis representations to project the screened Coulomb interaction: the Wannier and the muffin-tin basis functions. We investigate in detail the impact of the $V$ term for typical covalently bonded materials like graphene, for bulk semiconductors such as silicon and germanium, and for charge-transfer insulators like NiO. Our results demonstrate an improvement in accuracy of specific properties across these systems, providing a framework for describing materials with different interaction regimes. We compare our DFT$+U$$+V$ results using our cRPA parameter sets with (i) previous DFT$+U$$+V$ calculation employing pseudopotential approximations, (ii) with experimental results and (iii) with our $GW$ results.