Natural orbitals and two-particle correlators as tools for analysis of effective exchange couplings in solids

Abstract: Using generalizations of natural orbitals, spin-averaged natural orbitals, and two-particle charge correlators for solids, we investigate electronic structure of antiferromagnetic transition-metal oxides with a fully self-consistent, finite-temperature GW method. Our findings disagree with Goodenough-Kanamori (GK) rules, commonly used for qualitative interpretation of such solids. First, we found a strong dependence of natural orbital occupancies on momenta contradicting GK assumptions. Second, along the momentum path, the character of natural orbitals changes. In particular, contributions of oxygen 2s orbitals are important, which has not been considered in the GK rules. To analyze the influence of electronic correlation on the values of effective exchange coupling constants, we use both natural orbitals and two-particle correlators and show that electronic screening modulates the degree of superexchange by stabilizing the charge-transfer contributions, greatly affecting these coupling constants. Finally, we give a set of predictions and recommendations regarding the use of density functional, Green's function, and wave-function methods for evaluating effective magnetic couplings in molecules and solids.