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Mechanistic insights of the interaction among the energetic oxygen ions with nanosized ZnFe2O4: XAS-XMCD investigations

Abstract

Energetic ion interaction with multi-cation compounds and it's consequences on the local electronic structure amendments, which may facilitate intriguing O-2p and metal-d orbital hybridization and magnetic ordering, are the matter of debate and require a deep understanding of energy-transfer processes and magntic exchange mechanism. In this study, nanocrystals of ZnFe2O4 were subjected to O7+ ions of 100 MeV energy to understand, qualitatively and quantitatively, the metal-ligand field interaction, cation migration and magnetic exhange interaction by applying the X-ray absorption fine structure measurements and X-ray magnetic circular dichroism to get deeper mechanistics insights. The nanosized zinc ferrite nanoparticles (NP) of size ~ 16 nm, synthesized in cubic spinel phase, exhibit deterioration in crystalline phase when 100 MeV O7+ ions passes through them. However, size of these NPs remains almost same. The beheviour of crytsalline deterioration is associated with heat confinement in this interaction. The confined enery inside the nanoparticle promotes cation redistribution as well as the modification of local electronic structure. Prior to this interaction, almost 42% of Zn2+ ions occupy A-O4 tetrahedra, however, this value increases to 63% after interaction. An inverse effect is observed for metal ion occupancies at B-O6 octahedra. Fe and Zn L-edge spectra reveal that spin and valence states of metal ions do not affected by this interaction. This effect is also supported by the Fe K and Zn K-edge measurments. t2g/eg intensity ratio in the O K-edge spectra reduces after this interaction and is associated with de-attachemnet of Zn2+ ions from lattice. Extent of hybridization estimated from the ratio of post-edge to pre-edge region of O K-edge spectra reduces after this interaction. Metal-oxygen and metal-metal bond lengths get modified as a result of this interaction as determined from Extended X-ray absorption fine structure measurements. These measurements further supports the observation of cation migration from A-O4 octahedra to A-O6 octahedra and vice-versa. The Fe L-edge magnetic circular dichroism envisages that Fe3+ occupying sites A-O4 tetrahedra and B-O6 octahedra exhibit antiferromagnetic like ordering prior to this interaction. The energetic O ion interacted with NPs shows different kind of magnetic ordering.

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Publication details

The article was received on 17 Jan 2018, accepted on 03 Apr 2018 and first published on 03 Apr 2018


Article type: Paper
DOI: 10.1039/C8CP00368H
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
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    Mechanistic insights of the interaction among the energetic oxygen ions with nanosized ZnFe2O4: XAS-XMCD investigations

    J. P. Singh, B. Kaur, A. Sharma, S. H. Kim, S. Gautam, R. C. Srivastava, N. Goyal, W. C. Lim, H. Lin, J. Chen, A. K, D. Kanjilal, S. O. Won, I. J. Lee and K. H. Chae, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C8CP00368H

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