A charge‐transfer contribution to the g∥ shift of d7 ions in strong field situations

It is shown here that a good insight into the g∥ shift of d7 ions in elongated D4h symmetry requires one to go beyond the crystal field approach and consider the levels arising from a molecular orbital picture. Within this scheme is demonstrated the appearance of a second order contribution to the g∥ shift which depends on the spin‐orbit coefficient and the covalency of equatorial ligands. This new contribution can reasonably account for the positive g∥ shift observed for Pd3+ and Rh2+ doped silver halides. Furthermore, the smallness of the spin‐orbit coefficient of equatorial ligands in cases such as [Rh(CN)4Cl2]3− or [Fe (CN)4Cl2]5− is consistent with the slightly negative g∥ shift observed for these systems.

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