Solution

ID: past-exam-of-the-chemistry-course-of-the-year-4-of-the-natural-sciences-course-of-the-university-of-cambridge/2022/paper-1/2/b/ii/solution

Formal ionic counting gives La(III), N(−III), and therefore Re(VI), with a configuration. An isolated localized center would carry a saturation magnetic moment of order , much larger than the value quoted. It is not a ion made diamagnetic simply by an octahedral ligand field.
The spatially extended Re orbitals overlap strongly with N orbitals. Re–N interactions raise the -derived antibonding states, while interactions mix the states with the nitrogen network. Repetition through corner-sharing octahedra turns these combinations into broad energy bands. The nominal electron occupies a delocalized, partially filled band rather than an isolated magnetic orbital.
Only electrons close to the Fermi energy change their occupations appreciably in an applied magnetic field. Consequently a Pauli paramagnetism has a small, nonzero field-induced magnetization:
when is the density of states including both spin directions, expressed per formula unit and per unit energy. This band model explains a very small moment without requiring the absence of electrons in the Re-derived band. The reported material has metallic transport and a Pauli-like response.[ref]
The description “saturated” in the question should not be interpreted as complete alignment of one localized spin per Re: a nearly linear metallic response over a laboratory field range need not be a true fully spin-polarized saturation moment.

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