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Exotic quasiparticle states have been proposed in mixed-valent compounds exhibiting valence transitions. However, clear spectroscopic evidence identifying these states has remained elusive. Using synchrotron-based hard x-ray and extreme ultraviolet photoemission spectroscopy, we have probed the Tm 3d and 4f emissions in TmSe_{1-x}Te_{x}, where a Te concentration-dependent semimetal-insulator transition occurs alongside the valence transition. Our photoemission results, which are characteristic of the bulk, track this combined transition across the critical concentration (x_{c}=0.29). Notably, our results reveal a noninteger valence for the insulating phase and a novel quasiparticle excitation in the semimetallic phase: a Holstein polaron that extends beyond the standard periodic Anderson model.
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