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The localized-to-itinerant transition of f electrons lies at the heart ofheavy-fermion physics, but has only been directly observed in single-layerCe-based materials. Here, we report a comprehensive study on the electronicstructure and nature of the Ce 4f electrons in the heavy-fermion superconductorCe2PdIn8, a typical n=2 CenMmIn3n+2m compound, using high-resolution and 4d-4fresonance photoemission spectroscopies. The electronic structure of thismaterial has been studied over a wide temperature range, and hybridizationbetween f and conduction electrons can be clearly observed to form a Kondoresonance near the Fermi level at low temperatures. The characteristictemperature of the localized-to-itinerant transition is around 120K, which ismuch higher than its coherence temperature Tcoh~30K.

Electronic structure and 4f-electron character in Ce2PdIn8 studied by angle-resolved photoemission spectroscopy