In the present work, nanocrystalline samples of compositions 〖Ni〗_x 〖Fe〗_(1-x) 〖Co〗_2 O_4 (x = 0.0, 0.25, 0.50, and 0.75) have been synthesized via co-precipitation method by annealing at 900 oC. The nanocrystalline samples of compositions Ni0.25Fe0.75Co2O4 (D0.25) and Ni0.5Fe0.5Co2O4 (D0.5) crystallize in a pure spinel phase, whereas Ni0.75Fe0.25Co2O4 (D0.75) show the existence of secondary phase of NiO, as confirmed by the X-ray diffraction analysis. The particle size and lattice strain in the samples both decrease as Ni substitution is increased. The field-dependent dc magnetization M(H) virgin curve measured at 5 K for sample D0.75 shows the existence of field-induced metamagnetic transition, while this behavior is absent in samples D0.5 and D0.25. Dynamic magnetic properties have been investigated by ac susceptibility measurement, which shows a strong frequency dependence behavior resulting from the blocking/spin-glass freezing states depending upon the amount of Ni substitution and the range of measurement temperature. High-resolution X-ray photoelectron spectroscopy (HR-XPS) analysis reveals the presence of mixed valence states of Fe2+/Fe3+, Co2+/Co+3, and Ni2+/Ni+3 in all samples. Using first principles-based Density Functional Theory (DFT) calculations with HSE06 exchange-correlation functional predicts the correct description of ground state which is ferrimagnetic and insulating in their inverse spinel case for D0.25, D0.5, and D0.75 samples that agreed well with our experimental observations. A closer look at the electronic structure near the Fermi level (EF) of Ni-doped samples suggests a typical Mott-Hubbard insulating state while it is found to be a mixture of charge-transfer and Mott-Hubbard insulating state for parent compound FeCo2O4. The obtained spin-dependent gap hierarchy can have possible application in spintronics. We have studied a detailed correlation between experiment and theory.
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