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    11.2 Valence: Integral, Mixed, 605: Charge Density Wave

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    Supriya
    This document discusses valence mixing in rare earth compounds. It first discusses that the ground state of rare earth compounds in the mixed valent regime is macroscopically degenerate, with many ways to distribute electrons over lattice sites and degenerate ionic states on each site, leading to increased entropy. It then notes that models of rare earth compounds neglect quantum mechanical mixing between f-electrons and conduction electrons, which is important. Hybridization processes allow an f-electron to become a conduction electron or vice versa.

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    11.2 Valence: Integral, Mixed, 605: Charge Density Wave

    Uploaded by

    Supriya
    12 views1 page
    This document discusses valence mixing in rare earth compounds. It first discusses that the ground state of rare earth compounds in the mixed valent regime is macroscopically degenerate, with many ways to distribute electrons over lattice sites and degenerate ionic states on each site, leading to increased entropy. It then notes that models of rare earth compounds neglect quantum mechanical mixing between f-electrons and conduction electrons, which is important. Hybridization processes allow an f-electron to become a conduction electron or vice versa.

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    General Document 195

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    This document discusses valence mixing in rare earth compounds. It first discusses that the ground state of rare earth compounds in the mixed valent regime is macroscopically degenerate, with many ways to distribute electrons over lattice sites and degenerate ionic states on each site, leading to increased entropy. It then notes that models of rare earth compounds neglect quantum mechanical mixing between f-electrons and conduction electrons, which is important. Hybridization processes allow an f-electron to become a conduction electron or vice versa.

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    12 views1 page

    11.2 Valence: Integral, Mixed, 605: Charge Density Wave

    Uploaded by

    Supriya
    This document discusses valence mixing in rare earth compounds. It first discusses that the ground state of rare earth compounds in the mixed valent regime is macroscopically degenerate, with many ways to distribute electrons over lattice sites and degenerate ionic states on each site, leading to increased entropy. It then notes that models of rare earth compounds neglect quantum mechanical mixing between f-electrons and conduction electrons, which is important. Hybridization processes allow an f-electron to become a conduction electron or vice versa.

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    11.

    2 Valence: Integral, Mixed, Nearly Integral 605

    Thus the t - J- alternation of the antiferromagnetic ground state of the


    positive-U model is mapped onto an alternating 6s2 - 63' charge order of
    the negative4 model. We conclude that the ground state of BaBiOs is a
    charge density wave. Since it amounts to an alternation of Bi3+ and Bi5+
    valence states, we may also speak about valence disproportionation. The ar-
    gument implies that (at sufficiently large IUl) the charge order is stabilized by
    a coupling t2/lUl.
    N

    The negative-U concept has a nice corolfary. Let us notice that the binding
    into singlet pairs (d-sites) is energetically favoured whether the band is half-
    filled or not. However, away from half-filling, the singlet pairs are free to move.
    This seems to be the recipe for a superconductorwith a small coherence length.
    And indeed, doped BaBiOs (notably, Bal-,K,BiOs [263]) is a representative
    of one of the classes of high-T, superconductors.

    11.2.2 Valence Mixing in Rare Earth Compounds


    For the rest of this chapter, we return to the study of positive-U systems
    whose zeroth order Hamiltonian is (11.1). In the mixed valent regimes,
    the ground state of 7d0)is macroscopically degenerate. Taking the
    example of 4fo-4f' mixing, there are Cinf ways to distribute the 4f1
    sites over the lattice, and the ground state entropy is further increased
    by the fact that each 4f1 site has a degenerate ionic ground state.
    The most significant omission in writing down (11.1) is that it ne-
    glects any quantum-mechanical mixing between the f-electrons and the
    conduction electrons. In reality, the two sorts of electron states are
    hybridized. The complete Hamiltonian should include at least the one-
    electron hybridization processes'' which turn an f-electron into a con-
    duction electron, or vice versa

    To see the effect of switching on %hyb, let us consider the two con-
    secutive hybridization processes shown in Fig. 11.3. We envisage a
    "The notation Vk& for the hybridization amplitude is very slipshod. Properly
    written, it should make it clear that hybridization satisfies the requirements of sym-
    metry. Furthermore, some off-diagonal Coulomb processes also hybridize. However,
    we do not need the detailed form here.

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