Mass enhancement in 3d and s-p perovskites from symmetry breaking

TL;DR

This paper demonstrates that symmetry-breaking effects in mean-field DFT calculations can account for the observed mass enhancement in various 3d and s-p perovskites, challenging the notion that strong correlations are solely responsible.

Contribution

It shows that including symmetry-breaking distortions in DFT calculations reveals mass enhancement effects previously attributed to strong electronic correlations.

Findings

Symmetry-breaking in DFT explains mass enhancement in perovskites.

Mass enhancement occurs in both metals and insulators.

Symmetry effects contribute significantly to effective mass increases.

Abstract

In some d-electron oxides the measured effective mass m(exptl) has long been known to be significantly larger than the model effective mass m(model) deduced from mean-field band theory, i.e., m(exptl) = beta * m(model), where beta > 1 is the "mass enhancement", or "mass renormalization" factor. Previous applications of density functional theory (DFT), based on the smallest number of possible magnetic, orbital, and structural degrees of freedom, missed such mass enhancement, a fact that was taken as evidence of strong electronic correlation being the exclusive enabling physics. The current paper reports that known modalities of energy-lowering symmetry-broken spin and structural effects included in mean-field DFT show mass enhancement for both electrons and holes in a range of d-electron perovskites SrVO3, SrTiO3, BaTiO3, and LaMnO3 as well as p-electron perovskites CsPbI3 and SrBiO3, including metals (SrVO3) and insulators (the rest). This is revealed only when enlarged unit cells of the same parent global symmetry, which are large enough to allow for symmetry breaking distortions and concomitant variations in spin order, are explored for their ability to lower the total energy. The paper analyzes the contributions of different symmetry-broken modalities to mass enhancement, finds common effects in the range of d- as well as p-electron perovskites. Thus, symmetry breaking in mean-field theory could describe effects that were previously attributed exclusively to complex correlated treatments. Indeed, broken symmetries are often experimentally observed, e.g., octahedral tilting, Jahn-Teller distortions, or bond disproportionation, and often provide intuitive explanations in terms of degeneracy removal due to lowering of structural symmetry, or as shifting of band energies in explainable directions.