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The f-electron states of the heavy-fermion superconductor NpPd5Al2 were clarified from the systematic studies of the rare-earth and actinide based isostructural family. We found nearly trivalent Np3+ with 5f4 configuration at the boundary of the valence crossover, which may play an important role for the heavy-fermion superconductivity. We propose the pseudo-triplet ground state with

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