Local symmetry breaking and orbital glass behaviour in CoFe2O4

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Main Authors: Behera, Soumya Shephalika, Isha, Yogi, Arvind Kumar, Medicherla, V R Rao, Rajput, Parasmani, Sagdeo, Archana, Singh, Jaspreet, Sathe, Vasant, Choudhary, R J
Format: Preprint
Published: 2025
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author Behera, Soumya Shephalika
Isha
Yogi, Arvind Kumar
Medicherla, V R Rao
Rajput, Parasmani
Sagdeo, Archana
Singh, Jaspreet
Sathe, Vasant
Choudhary, R J
author_facet Behera, Soumya Shephalika
Isha
Yogi, Arvind Kumar
Medicherla, V R Rao
Rajput, Parasmani
Sagdeo, Archana
Singh, Jaspreet
Sathe, Vasant
Choudhary, R J
contents The structural distortions, orbital correlations, and electronic states in cobalt ferrite (CoFe2O4) were investigated using complementary characterisation techniques, including SR-XRD, HAXPES, XANES, EXAFS, and Raman spectroscopy. SR-XRD confirms phase purity and reveals a temperature-dependent superlattice reflection between 200 K and 100 K, consistent with the emergence of short-range orbital ordering driven by cooperative Jahn-Teller distortion (JTD). The disappearance of this feature below 100 K signals orbital freezing and the onset of a glass-like orbital state. HAXPES measurements show multiplet splitting and charge-transfer satellite features in the Co and Fe 2p core levels, indicating mixed valence states and strong electron correlations. XANES analysis reveals hybridized p-d states and local coordination distortions. Temperature-dependent EXAFS measurements indicate increasing local disorder-particularly in Fe-O and Fe-Fe octahedral bonds as evidenced by enhanced Debye-Waller factors. These distortions, attributed to cation redistribution and oxygen vacancies, are static and asymmetric, primarily affecting the octahedral sublattice. Notably, signatures of cooperative Jahn-Teller distortions emerge in the intermediate temperature range (200-100 K) and disappear upon further cooling. Raman spectroscopy further supports these findings, revealing phonon anomalies and enhanced spin-phonon coupling in the same temperature range. Magnetic measurements indicate spin reorientation and exchange interaction anomalies that align with the orbital behaviour. Together, these results hint at a frustrated orbital state in CoFe2O4 possibly involving cooperative Jahn-Teller distortions, disrupted long-range coherence, and orbital glass behaviour offering new insights into the coupling of orbital, spin, and lattice degrees of freedom in spinel systems.
format Preprint
id arxiv_https___arxiv_org_abs_2506_16857
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Local symmetry breaking and orbital glass behaviour in CoFe2O4
Behera, Soumya Shephalika
Isha
Yogi, Arvind Kumar
Medicherla, V R Rao
Rajput, Parasmani
Sagdeo, Archana
Singh, Jaspreet
Sathe, Vasant
Choudhary, R J
Strongly Correlated Electrons
The structural distortions, orbital correlations, and electronic states in cobalt ferrite (CoFe2O4) were investigated using complementary characterisation techniques, including SR-XRD, HAXPES, XANES, EXAFS, and Raman spectroscopy. SR-XRD confirms phase purity and reveals a temperature-dependent superlattice reflection between 200 K and 100 K, consistent with the emergence of short-range orbital ordering driven by cooperative Jahn-Teller distortion (JTD). The disappearance of this feature below 100 K signals orbital freezing and the onset of a glass-like orbital state. HAXPES measurements show multiplet splitting and charge-transfer satellite features in the Co and Fe 2p core levels, indicating mixed valence states and strong electron correlations. XANES analysis reveals hybridized p-d states and local coordination distortions. Temperature-dependent EXAFS measurements indicate increasing local disorder-particularly in Fe-O and Fe-Fe octahedral bonds as evidenced by enhanced Debye-Waller factors. These distortions, attributed to cation redistribution and oxygen vacancies, are static and asymmetric, primarily affecting the octahedral sublattice. Notably, signatures of cooperative Jahn-Teller distortions emerge in the intermediate temperature range (200-100 K) and disappear upon further cooling. Raman spectroscopy further supports these findings, revealing phonon anomalies and enhanced spin-phonon coupling in the same temperature range. Magnetic measurements indicate spin reorientation and exchange interaction anomalies that align with the orbital behaviour. Together, these results hint at a frustrated orbital state in CoFe2O4 possibly involving cooperative Jahn-Teller distortions, disrupted long-range coherence, and orbital glass behaviour offering new insights into the coupling of orbital, spin, and lattice degrees of freedom in spinel systems.
title Local symmetry breaking and orbital glass behaviour in CoFe2O4
topic Strongly Correlated Electrons
url https://arxiv.org/abs/2506.16857