Exchange interactions in antiferromagnetic salts of iridium. I. Paramagnetic resonance experiments

Paramagnetic resonance methods have been used to investigate Ir-Ir exchange interactions in K 2 IrCl 6 and (NH 4 ) 2 IrCl 6 . Measurements are described of the resonance spectrum from nearest-neighbour pairs of Ir ions in semi-dilute mixed crystals where Pt is substituted for Ir. The results show that the isotropic p art of the Ir-Ir exchange, J / k , is antiferromagnetic and of magnitude 11.5 ± 1°K and 7.5 ± 1°K for the potassium and ammonium salts, respectively. There is also found to be an anisotropic part with rhombic symmetry and with magnitude of order 1 cm -1 . No lines attributable to next-nearest-neighbour pairs were found, and it is suggested that this interaction is small. The results are com pared briefly with the magnetic susceptibility experiments of Cooke et al . (part II) who find that the concentrated salts go antiferromagnetic in the liquid-helium temperature range, and also with the theoretical analysis of the superexchange mechanism given by Judd (part III).

Measurements have been made of the magnetic susceptibilities of ammonium and potassium chloroiridates at temperatures between room temperature and 1°K. The results obtained at high temperatures have been analysed into a susceptibility following a Curie-Weiss law together with temperature-independent terms. The values of the isotropic exchange inter­actions between neighbouring iridium ions deduced from the Weiss constant agree well with those calculated from paramagnetic resonance measurements. At lower temperatures the magnetic susceptibilities become almost independent of temperature over a certain range and then fall sharply at the antiferromagnetic transtion points (2.16 °K for the ammonium salt, 3.08°K for the potassium salt). These results are discussed in term s of the exchange interaction between nearest- and next-nearest-neighbour iridium ions.


Unexpected lines in the acoustic paramagnetic resonance spectrum of KMgF 3 :Ni 2+ are assigned to second nearest neighbour and more distant Ni 2+ ion pairs. Exchange parameters are deduced for the pairs, and the mechanism for their spin-phonon interaction is inferred to be the single-ion, ( S 1 . d . S 1 ) + ( S 2 - d . S 2 ) process.


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