The DFT + U method in the linear combination of Gaussian-type orbitals framework: Role of 4f orbitals in the bonding of LuF3

Using the DFT + U methodology with a localized basis set, we studied the role of Lu 4f orbitals in the bonding of LuF3. We carried out scalar relativistic all-electron Douglas–Kroll–Hess DFT calculations of geometry, atomization energy, and vertical ionization potentials without and with the Hubbard term. The on-site repulsion parameter Ueff for Lu 4f orbitals was estimated from reference atomic data. With Ueff > 0, atomic localization of the valence 4f-like molecular orbitals is recovered, thus removing the spurious mixing of Lu 4f and F 2p orbitals present in standard Kohn–Sham calculations, while the molecular properties of LuF3 remained unchanged.