Role of p-d Hybridization in Structural Transition and Magnetic Properties of Co-substituted Mn3O4: X-ray Absorption Spectroscopy Study

Published

February 8, 2024

Author(s)

G. Dwivedi, S.M. Kumawat, Y.Y. Chin, Jeffrey Lynn, Hsiung Chou

Abstract

This work investigates the role of p-d orbital hybridization in the structural transition from tetragonal I41/amd to cubic Fd3 ̅m and enhancement in Néel temperature (TN) from 43K to 175K in Co-substituted (Mn1-xCox)3O4 (where x = 0.0, 0.1, 0.2, 0.3, 0.5, and 0.6). X-ray absorption spectra of Co-L2,3 and Mn-L2,3 edges show that the high-spin Co2+ cations initially substitute the Mn2+ at the tetrahedral-sites. When the tetrahedral-sites are fully occupied, then the high-spin Co3+ cations begin to occupy the octahedral-site. The substitution of Co cations at both the tetrahedral and octahedral-sites increases the bond angle between adjacent tetrahedral and octahedral site cations via O-2p orbitals, suppressing the orbital instability of Mn3+ cations. These effects dramatically enhance the superexchange interaction and hence the TN.

Citation

Journal of Alloys and Compounds

Volume

981

Pub Type

Journals

Download Paper

https://doi.org/10.1016/j.jallcom.2024.173651

Local Download

Keywords

Spinel material, Geometric Frustration, Doping Effect

Citation

Dwivedi, G. , Kumawat, S. , Chin, Y. , Lynn, J. and Chou, H. (2024), Role of p-d Hybridization in Structural Transition and Magnetic Properties of Co-substituted Mn3O4: X-ray Absorption Spectroscopy Study, Journal of Alloys and Compounds, [online], https://doi.org/10.1016/j.jallcom.2024.173651, https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=956986 (Accessed October 14, 2024)