Cation and Spin Interactions in Cadmium Ferrite: A Quantum Mechanical Study

镉铁氧体中阳离子和自旋相互作用:量子力学研究

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Abstract

Spinel ferrites have emerged as fascinating materials, not just for their diverse functionalities, but for the dynamic structural transformations they undergo under varying conditions. These phase transitions, often subtle yet deeply influential, play a pivotal role in tuning their electronic, magnetic, and vibrational properties. At the heart of this complexity lies the versatile arrangement of divalent and trivalent cations between the tetrahedral (A) and octahedral (B) sites, giving rise to a rich spectrum of magnetic interactions, charge dynamics, and lattice responses. This intricate cation interplay makes spinel ferrites a playground for exploring structure-property relationships in advanced functional materials. In this study, we investigated the structural, vibrational, and magnetic properties of Cd ferrite using advanced hybrid functionals (B3LYP, HSE06, and PBE0). Our calculations reveal that the normal spinel phase is the most stable configuration, with minimal energy differences between spin arrangements (~0.005-0.008 eV) and slightly larger differences when including zero-point energy (~0.023 eV). All the investigated structures exhibit a semiconducting nature, with band gaps varying depending on the spin arrangements. The IR and Raman spectra highlight the influence of spin ordering on vibrational modes. The simulations of the Raman spectra demonstrate that both the frequencies and intensities of the Raman peaks strongly depend on the magnetic ordering. The present theoretical study offers a consistent framework for assigning vibrational modes, which may help resolve ambiguities and contribute to a deeper understanding of the vibrational properties of Cd ferrite. These findings provide a robust foundation for further experimental and computational exploration of this material.

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