Modelling Magnetic Multipolar Phases in Density Functional Theory

TL;DR

This paper introduces a method to model complex magnetic multipolar phases in correlated insulators using Density Functional Theory with an educated constrained initialisation, enabling the study of exotic magnetic ground states like ferro-octupolar order.

Contribution

It presents a novel approach to accurately capture magnetic multipolar phases in DFT+U by using an initial density matrix derived from an ab initio effective Hamiltonian.

Findings

Successfully models ferro-octupolar ground state in Ba₂MOsO₆

Demonstrates the method's ability to access properties of exotic magnetic states

Shows improved reliability over conventional DFT+U approaches

Abstract

Multipolar magnetic phases in correlated insulators represent a great challenge for Density Functional Theory (DFT) due to the coexistence of intermingled interactions, typically spin-orbit coupling, crystal field and complex non-collinear and high-rank inter-site exchange, creating a complected configurational space with multiple minima. Though the +U correction to DFT allows, in principle, the modelling of such magnetic ground states, its results strongly depend on the initially symmetry breaking, constraining the nature of order parameter in the converged DFT+U solution. As a rule, DFT+U calculations starting from a set of initial on-site magnetic moments result in a conventional dipolar order. A more sophisticated approach is clearly needed in the case of magnetic multipolar ordering, which is revealed by a null integral of the magnetization density over spheres centered on magnetic atoms, but with non-zero local contributions. Here we show how such phases can be efficiently captured using an educated constrained initialisation of the onsite density matrix, which is derived from the multipolar-ordered ground state of an ab initio effective Hamiltonian. Various properties of such exotic ground states, like their one-electron spectra, become therefore accessible by all-electron DFT+U methods. We assess the reliability of this procedure on the Ferro-Octupolar ground state recently predicted in Ba$_2$MOsO$_6$ (M = Ca, Mg, Zn) [Phys. Rev. Lett. 127, 237201 (2021)]