1D transition metal oxide chains as a challenging model for <i>ab initio</i> calculations

Abstract

Providing highly simplified models of strongly correlated electronic systems that challenge ab initio calculations can serve as a valuable testing ground to improve these methods. In this study, we present a comprehensive investigation of the structural, magnetic, and electronic properties of one-dimensional transition metal mono-oxide chains (VO, CrO, MnO, FeO, CoO, and NiO) using density functional theory (DFT), DFT+U, and coupled-cluster singles and doubles (CCSD) calculations. The Hubbard U parameter for DFT+U is determined using linear response theory. In all systems studied except MnO, the presence of multiple local minima—primarily due to the electronic degrees of freedom associated with the d-orbitals—leads to significant challenges for DFT, DFT+U, and Hartree–Fock methods in finding the global minimum in ab initio calculations. Our results indicate that the antiferromagnetic (AFM) state is energetically favored for all chains, except CrO, when using DFT+U and the Perdew–Burke–Ernzerhof (PBE) functional. Analysis of the band structures shows that while PBE often predicts metallic or half-metallic FM states, DFT+U opens band gaps and correctly yields insulating behavior in all cases. Furthermore, we compared the energy differences between the AFM and FM states using DFT+U and CCSD for CrO, MnO, FeO, CoO, and NiO. Our findings indicate that CCSD predicts larger energy differences in some cases compared to DFT+U, suggesting that the Hubbard U parameter obtained through linear response theory may be overestimated when used to calculate energy differences between different magnetic states. For CrO, CCSD predicts an AFM ground state, in contrast to the predictions from DFT+U and PBE methods.