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Spin-State Transition in LaCoO3 and Related Materials

  • Chapter
Spin Crossover in Transition Metal Compounds II

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 234))

Abstract

Of the several inorganic systems that exhibit spin-state transitions, LaCoO3 and related cobaltates represent an important category of oxides exhibiting a transition from the low-spin (LS) state to a state of higher spin with increasing temperature. It was first considered that the transition was from the LS (1A1) to the high-spin (HS, 5T2) state and a variety of investigations were performed on this transition by employing magnetic susceptibility, Mössbauer spectroscopy, NMR spectroscopy and other measurements. These studies not only showed the evolution of the high-spin state with temperature but also the ordering of the two spin states and other related phenomena. The spin-gap energy in LaCoO3 is smaller than the charge-gap energy. The transition temperature varies depending on the rare earth ion in the LnCoO3 series. In recent years, it has been demonstrated that the spin-state transition in LaCoO3 occurs initially from the LS state to the intermediate spin (IS, 3T1) state rather than to the HS state with increase in temperature. The intermediate spin-state Co3+ is a Jahn-Teller (JT) ion. The spin-state transition is therefore associated with lattice distortion, which is readily studied by infrared spectroscopy. Raman spectroscopy yields valuable information on the spin-state transition. Electronic structure calculations have been performed and the results verified experimentally by photon emission spectroscopy and other techniques. Recent studies indicate that it may be necessary to employ a three spin-state (LS-IS-HS) model rather than a two spin-state (LS-IS) model to fully explain the observed transition. Several theoretical models have been proposed to explain the spin-state transition in LaCoO3. These include the singlet-triplet transition model, the two-sublattice model, and the two-phonon model. The effect of hole doping on the spin-state transition has been examined in compounds like La1-xSrxCoO3. In this article, we discuss the various experimental and theoretical studies of LaCoO3 and related cobaltates.

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Acknowledgements

The authors thank BRNS (DAE) for supporting this research. One of us (M. M. S.) thanks CSIR (India) for a fellowship.

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Authors and Affiliations

  1. Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur P.O., 560-064, Bangalore, India

    C. N. R. Rao, M. Motin Seikh & Chandrabhas Narayana

  2. Solid State and Structural Chemistry Unit, Indian Institute of Science, 560-012, Bangalore, India

    C. N. R. Rao & M. Motin Seikh

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  1. C. N. R. Rao
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  2. M. Motin Seikh
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  3. Chandrabhas Narayana
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Correspondence to C. N. R. Rao .

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Rao, C.N.R., Seikh, M.M., Narayana, C. Spin-State Transition in LaCoO3 and Related Materials. In: Spin Crossover in Transition Metal Compounds II. Topics in Current Chemistry, vol 234. Springer, Berlin, Heidelberg. https://doi.org/10.1007/b95410

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  • DOI: https://doi.org/10.1007/b95410

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-40396-8

  • Online ISBN: 978-3-540-36774-1

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