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  • 3.5 Spatting of A: Hand

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    1) Cobalt and iron ions in a cubic crystal field can exist in either a high-spin or low-spin state depending on whether the intra-atomic exchange energy favors a higher or lower spin configuration. 2) In some materials like LiCoO2, the cobalt ion is found to be in the stable low-spin state, while in other materials the high-spin state is stable. 3) For manganese ions in materials like LaMnO3, the large crystal field splitting leads to a clear distinction between core and lightly bound electrons.

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    General Document 81

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    1) Cobalt and iron ions in a cubic crystal field can exist in either a high-spin or low-spin state depending on whether the intra-atomic exchange energy favors a higher or lower spin configuration. 2) In some materials like LiCoO2, the cobalt ion is found to be in the stable low-spin state, while in other materials the high-spin state is stable. 3) For manganese ions in materials like LaMnO3, the large crystal field splitting leads to a clear distinction between core and lightly bound electrons.

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    11 views1 page

    3.5 Spatting of A: Hand

    Uploaded by

    Kamleshkekane1
    1) Cobalt and iron ions in a cubic crystal field can exist in either a high-spin or low-spin state depending on whether the intra-atomic exchange energy favors a higher or lower spin configuration. 2) In some materials like LiCoO2, the cobalt ion is found to be in the stable low-spin state, while in other materials the high-spin state is stable. 3) For manganese ions in materials like LaMnO3, the large crystal field splitting leads to a clear distinction between core and lightly bound electrons.

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    of 1

    3.

    5 Spatting of a d-Level in Cubic Field 99

    Fi e 3.5: Left and middle: High-spin and law-spin configurations of a CoS+ (or
    P
    Fe +) ion in cubic environment. Right: In LaMnO3, the Mn3+ ion preserves its high-
    spin state but the large crystal field splitting leads to a clear disctinction between
    “core” ( t s o ) and “lightly bound* (eg) electrons.

    would predict the configuration t&ei, with S = 2; we may call this the
    high-spin state (Fig. 3.5). On the other hand, with six &electrons one
    can just fill the t2, level, thereby avoiding the occupation of eg states.
    The configuration t!g goes with S = 0; this is the low-spin state. The
    t2,-eg gap is the largest of crystal-field splittings, and it is apparently
    large enough to compete with the intra-atomic exchange energy which
    favours S = 2. In nature, sometimes the high-spin state, and some-
    times the low-spin state is found to be stable. A careful investigation
    of LiC002 provided a clear-cut case of the low-spin state of Co3+ [421].
    We may ask whether the competition between high-spin and low-
    spin states does not extend to the 3d7 configuration where S = 3/2
    is the high spin and S = 1/2 would be the low spin. Indeed it has
    been suggested that Ni3+ is in its S = 112 low-spin state in the curious
    antifmomagnet LiNiO2.
    The perovskite Lac003 is an interesting system where the low-spin
    and high-spin configurations have comparable stability, and therefore
    both are seen in the range of accessible temperatures. Given that the
    low-spin configuration is slightly lower in energy (which seems to be the
    cme), we. can think of at least two reasons why the high-spin configu-
    ration should appear in large concentration at elevated temperatures.
    One irr the large spin entropy associated with S = 2. Another is that as
    soon aa the ions acquire spin, they can gain energy from spin-spin inter-
    actions, or may even order magnetically. We may be wondering whether

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