No source-free exchange-correlation magnetic fields in non-collinear spin-density functional theory

Abstract

The source-free condition, $\nabla\cdot\mathbf{B}_{xc}=0$, where $\mathbf{B}_{xc}$ is the exchange-correlation (xc) magnetic field in non-collinear spin-density functional theory, is widely believed to be exact. Recent studies report that when the field of a parent functional is made source-free by projection - a posteriori, rather than by construction - the predicted magnetic moments improve. We show that the condition violates global spin-rotation symmetry of the xc energy functional $E_{xc}$ and therefore cannot be exact. It has nonetheless been found useful, so we examine the errors it introduces. We first implement the condition variationally, using any parent $E_{xc}$ functional: the resulting source-free (SoF) field is divergence-free, remains a functional derivative, and exerts local torques. With the LSDA as the parent functional, we examine Mn$_2$. SoF and the locally collinear (LoC) LSDA both give too short a bond and too large a bond energy, but they differ on the magnetic and electronic properties: SoF finds the experimentally observed $^1Σ_g^+$ antiferromagnet, with a coupling of the right sign and, extrapolated to the experimental bond length, roughly the right size, while LoC finds a high-spin $^{11}Π_u$ ferromagnet and the wrong sign. But breaking the symmetry produces severe errors in every directional property. A rigid spin rotation of the magnetization changes $E_{xc}$ by about 1 eV (it should not change at all); in a weak uniform external field the magnetization points perpendicular to the field (it should be antiparallel to it); and the system develops a spurious magnetic anisotropy of about 175 meV (an effect that requires spin-orbit coupling, which is absent here).