Ab Initio Full Cell GW+DMFT for Correlated Materials

Abstract

The quantitative prediction of electronic properties in correlated materials requires simulations without empirical truncations and parameters. We present a method to achieve this goal through a new ab initio formulation of dynamical mean-field theory (DMFT). Instead of using small impurities defined in a low-energy subspace, which require complicated downfolded interactions which are often approximated, we describe a full cell GW+DMFT approach, where the impurities comprise all atoms in a unit cell or supercell of the crystal. Our formulation results in large impurity problems, which we treat here with efficient quantum chemistry impurity solvers that work on the real-frequency axis, combined with a one-shot G₀W₀ treatment of long-range interactions. We apply our full cell approach to bulk Si, two antiferromagnetic correlated insulators NiO and α−Fe₂O₃, and the paramagnetic correlated metal SrMoO₃, with impurities containing up to ten atoms and 124 orbitals. We find that spectral properties, magnetic moments, and two-particle spin correlation functions are obtained in good agreement with experiment. In addition, in the metal oxide insulators, the balanced treatment of correlations involving all orbitals in the cell leads to new insights into the orbital character around the insulating gap.