Solution

ID: past-exam-of-the-chemistry-course-of-the-year-4-of-the-natural-sciences-course-of-the-university-of-cambridge/2022/paper-2/section-b/21/e/solution

Define . Each site has exchange-connected neighbours. In mean-field theory, replacing neighbours by their mean spin produces the effective field that yields
Thus
for Mn, Fe, Co and Ni. Negative means antiferromagnetic exchange in this convention; a Hamiltonian written with instead of would have twice these numerical values. The increasingly negative values indicate a growing effective exchange energy, although different orbital occupancy and anisotropy mean that they are not a simple universal function of -electron number.
A three-dimensional six-connected framework is more favourable to mean-field reasoning than isolated chains, but the theory neglects short-range correlations, anisotropic exchange and fluctuations. The ratios show substantial departures from the simplest unfrustrated isotropic mean-field relation. The values are therefore effective high-temperature exchange estimates, not a complete microscopic fit to the ordered phases.

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