The paramagnetic resonance spectrum of copper acetate is anomalous in that it resembles that of an ion of spin 1, and its intensity decreases as the temperature is lowered. The latter is correlated with the decreasing susceptibility found by Guha (1951). The following hypo­theses are suggested: (1) the crystalline field acting on each copper ion is similar to that in other salts such as the Tutton salts; (2) isolated pairs of copper ions interact strongly through exchange forces, each pair forming a lower singlet state and an upper triplet state, the latter only being paramagnetic. On this basis both the fine structure and the hyperfine structure of the spectrum have a simple explanation, and the theory also predicts a small initial split­ting of the triplet state of the same order as that found experimentally. The unit cell of the crystal contains two differently oriented pairs of ions, and, using an empirical value for the exchange parameter, fair agreement with the susceptibility measurements of Guha is obtained.

Anomalous Paramagnetism of Copper Acetate

Publisher Summary This chapter discusses that the subject of exchange in magnetic materials is divided into two parts, referring to insulators and to metals. This distinction is useful from the magnetic point of view because in insulators the spins and magnetic moments whose alignments lead to magnetic effects are certainly localizable so that phenomenologically is described by a spin Hamiltonian that contains spin operators and exchange terms of Heisenberg type. It discusses that there is relationship among the mechanisms important in metals, such as conduction electron polarization, and those in insulators. The chapter provides historical discussion of the subjects of antiferromagnetism and of exchange in insulators. It focuses on the Heisenberg Hamiltonian, with a brief derivation and a discussion of some of the statistical theories of magnetism based upon it, primarily molecular field theory, which is by far the most generally useful in the experimental measurement of exchange. The chapter also describes older theories and presents ideas about super-exchange, and gives a discussion and a diagrammatic classification of all the possible higher-order processes.

Theory of Magnetic Exchange Interactions:Exchange in Insulators and Semiconductors

Publisher Summary There have been many reviews and books on electron spin resonance (ESR) and several on transition metal ions. Many of these publications have been written by physicists or theoreticians and are very comprehensive. This review is aimed at inorganic chemists, who have had no experience relating to electron spin resonance and who are becoming more and more likely either to use the technique or to need to appreciate the significance of the information available from the technique. The first part of the review gives an elementary account of the relevant theory. There are many good books for further reading for the inorganic chemist, who wishes to go deeper into the subject. The second part of the review is a comprehensive survey of the results of ESR studies on compounds of transition elements. Inevitably, there has had to be some selection of material, and the criteria for inclusion or rejection has been based upon the likely interest of an inorganic chemist might have in the species. This is particularly in the areas, where there is a lot of related work, e.g., the Mn2+ host-lattice data. In the case of copper dg complexes, there has been much duplication of work and papers devoted to the spectra of complexes where a minor substitutive change has been made to a bulky organic ligand.

Electron Spin Resonance of Transition Metal Complexes

Mono-, bi-, tetra- and polynuclear copper(II) halogenocarboxylates

2 – Exchange in Insulators: Superexchange, Direct Exchange, and Double Exchange

(1952). Anomalous paramagnetism and exchange interaction in copper acetate. The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science: Vol. 43, No. 338, pp. 372-374.

K.D. Bowers

Papers

Anomalous paramagnetism and exchange interaction in copper acetate