Phase stability and properties of manganese oxide polymorphs: Assessment and insights from diffusion Monte Carlo

We present an analysis of the polymorphic energy ordering and properties of the rocksalt and zinc-blende structures of manganese oxide using fixed node diffusion Monte Carlo (DMC). Manganese oxide is a correlated, antiferromagnetic material that has proven to be challenging to model from first principles across a variety of approaches. Unlike conventional density functional theory and some hybrid functionals, fixed node diffusion Monte Carlo finds the rocksalt structure to be more stable than the zinc-blende structure, and thus recovers the correct energy ordering. Analysis of the site-resolved charge fluctuations of the wave functions according to DMC and other electronic structure descriptions gives insights into elements that are missing in other theories. While the calculated band gaps within DMC are in agreement with predictions that the zinc-blende polymorph has a lower band gap, the gaps themselves overestimate reported experimental values.