Sunday, 20 March 2016

physical chemistry - What is antisymmetric exchange? What is J-strain? Where does it come from?


I'm reading a paper1 by Sanakis, et al. that characterises the magnetic coupling in the $\ce{Fe3S4}$ clusters present in bacterial ferredoxin II and beef heart aconitase as arising through something called 'antisymmetric exchange'. This looks like it may be a result of the apparent magnetic frustration of the system (three high-spin $\ce{Fe^{3+}}$ ions, all in essentially identical environments, all antiferromagnetically coupled with respect to their neighbours). The paper says that the clusters have a S=1/2 ground state, which is incompatible with a broken-symmetry model.


The wikipedia article on antisymmetric exchange (all four sentences of it) is not particularly edifying. I'm hoping an expert can explain what antisymmetric exchange is and what causes it as I've not heard of it be before. The paper also notes that the exchange situation in the cluster gives rise to three slightly different $J_{ij}$ values (again, despite the symmetry of the ions) and terms this 'J-strain'. This makes me doubt that, for instance, 'antisymmetric' is being used as a synonym for 'antiferromagnetic'.


[Edit]


Here's an example of the general connectivity of this kind of $\ce{Fe3S4}$ cluster (based on D. Gigas FdII (PDB entry 1F2G)). The cluster comprises a hemicubane. $\ce{S_{Cys}}$ denotes a cysteinyl sulfur.


Fe3S4 cluster




(1) Sanakis, Y.; Macedo, A.L.; Moura, I.; Moura, J.J.G.; Papaefthymiou, V.; Münck, E.; Evidence for Antisymmetric Exchange in Cuboidal $\ce{[3Fe-4S]^+}$ Clusters; J. Am. Chem. Soc.; 2000, 122, pp. 11855-11863




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