Finite valence fluctuations

Up to now, we have concentrated on the physics at zero kelvin. In this section, we extend the studies to finite temperatures and discuss finite temperature phase diagrams. The physics at finite temperatures is dominated by thermal fluctuations between low lying excited states of the system. These fluctuations can include spin fluctuations, fluctuations between different valence states, or fluctuations between different orbitally ordered states, if present. Such fluctuations can be addressed througih a so-called alloy analogy. If there is a timescale that is slow compared to the motion of the valence electrons, and on which the configurations persist between the system fluctuations, one can replace the temporal average over all fluctuations by an ensemble average over all possible (spatially... 

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