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We report on strong dipole transitions to 3d orbitals of neighboring Co atomsin the Co 1s x-ray absorption pre-edge. They are revealed by applyinghigh-resolution resonant x-ray emission spectroscopy (RXES) to compoundscontaining CoO6 clusters. When contrasted to quadrupole local 1s3d excitations,these non-local 1s3d transitions are identified by their energy dispersion andangular dependence, their sensitivity to second-shell effects (i.e. theconnection mode of the CoO6 octahedra and the bond lengths), and an upwardsenergy shift of 2.5 eV due to the poorer screening of the core hole. Theexperiment reveals that the intensity of the non-local transitions gauges theoxygen-mediated 4p-O-3d intersite hybridization. We propose a revisedinterpretation of the pre-edges of transition metal compounds. Detailedanalysis of these new features in the pre-edge offers a unique insight in theoxygen mediated metal-metal interactions in transition metal-based systems,which is a crucial aspect in orbital ordering and related electronic andmagnetic properties. In addition, the exceptional resolving power of thepresent 1s2p RXES experiment allows us to demonstrate the coherent second-ordernature of the underlying scattering process.

Intersite 4p-3d hybridization in cobalt oxides: a resonant x-ray emission spectroscopy study