Charge disproportionation and collinear magnetic order in the frustrated triangular antiferromagnet AgNiO2

TL;DR

This study reveals charge order and collinear magnetic stripe order in AgNiO2, a frustrated triangular antiferromagnet, driven by charge fluctuations and orbital degeneracy lifting, with implications for understanding complex magnetic and electronic phases.

Contribution

It provides the first detailed neutron diffraction analysis showing charge disproportionation and collinear magnetic order in AgNiO2, highlighting the role of charge fluctuations and orbital effects.

Findings

Charge order occurs below 365 K, lifting orbital degeneracy.

Low-temperature magnetic order is a collinear stripe pattern.

Charge fluctuations may mediate the structural transition.

Abstract

We report a high-resolution neutron diffraction study of the crystal and magnetic structure of the orbitally-degenerate frustrated metallic magnet AgNiO2. At high temperatures the structure is hexagonal with a single crystallographic Ni site, low-spin Ni3+ with spin-1/2 and two-fold orbital degeneracy, arranged in an antiferromagnetic triangular lattice with frustrated spin and orbital order. A structural transition occurs upon cooling below 365 K to a tripled hexagonal unit cell containing three crystallographically-distinct Ni sites with expanded and contracted NiO6 octahedra, naturally explained by spontaneous charge order on the Ni triangular layers. No Jahn-Teller distortions occur, suggesting that charge order occurs in order to lift the orbital degeneracy. Symmetry analysis of the inferred Ni charge order pattern and the observed oxygen displacement pattern suggests that the transition could be mediated by charge fluctuations at the Ni sites coupled to a soft oxygen optical phonon breathing mode. At low temperatures the electron-rich Ni sublattice (assigned to a valence close to Ni2+ with S = 1) orders magnetically into a collinear stripe structure of ferromagnetic rows ordered antiferromagnetically in the triangular planes. We discuss the stability of this uncommon spin order pattern in the context of an easy-axis triangular antiferromagnet with additional weak second neighbor interactions and interlayer couplings.