DFT+U in Dudarev's formulation with corrected interactions between the electrons with opposite spins: The form of Hamiltonian, calculation of forces, and bandgap adjustments.

Abstract

Hubbard corrected density functional theory (DFT) methods, such as the DFT+U approach in Dudarev's approximation, are widely used for the description of energetics and electronic structure of strongly correlated materials, providing higher level of accuracy than local DFT calculations (e.g., local density approximation or generalized gradient approximation). However, the DFT+U method in Dudarev's formulation limits the introduced corrections to interactions between the electrons within the same spin channel, whereas interactions between the electrons with opposite spins are still treated using local DFT functional (e.g., Perdew-Burke-Ernzerhof). In recent years, the need for correction of these interactions between the electrons with opposite spins has been recognized and additional terms have been added to the Hubbard term to reflect it. Although such extended DFT+U functionals have been proposed, the form of respective Hamiltonian operator, defined as a total energy derivative over density with appropriate treatment of double counting corrections due to additional Hubbard terms, has not been explicitly presented. In this work, we provide an expression for such a type of Hamiltonian, which contains the respective double counting correction contributions. This formulation also allows evaluation of atomic forces, using computational settings discussed herein. In addition, we also introduce adjustments for too narrow theoretical bandgaps, using scissor operator technique. This allows for a greater level of corrections of energetics and magnetic properties of studied transition metal compounds, avoiding possible unphysical overlap between occupied and unoccupied electronic bands.