Local orbital degeneracy lifting as a precursor to an orbital-selective Peierls transition

Fundamental electronic principles underlying all transition metal compounds are the symmetry and filling of the d -electron orbitals and the influence of this filling on structural configurations and responses. Here we use a sensitive local structural technique, x-ray atomic pair distribution function analysis, to reveal the presence of fluctuating local-structural distortions at high temperature in one such compound, CuIr 2 S 4 . We show that this hitherto overlooked fluctuating symmetry-lowering is electronic in origin and will modify the energy-level spectrum and electronic and magnetic properties. The explanation is a local, fluctuating, orbital-degeneracy-lifted state. The natural extension of our result would be that this phenomenon is likely to be widespread amongst diverse classes of partially filled nominally degenerate d -electron systems, with potentially broad implications for our understanding of their properties.