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A cluster orbital theory is developed, which allows the calculation of Mössbauer spectra of oxidized and reduced ferredoxin of Clostridium pasteurianum under the conditions of low tempera­ ture (4.2 K) and high external magnetic field (H ex  &gt;̃ 1T) . The calculations are based on the symmetry properties of the problem and the way in which these symmetries are reflected in the (iron) 4 -sulfur cluster wave function. The assumed cubic T d  symmetry of the cluster implies an isotropic interaction with the applied external magnetic field, where the average g-tensor is taken to be g -1.944 in accordance with ESR results. The magnetic hyperfine interaction of the cluster electrons with the magnetic dipole moments of the iron nuclei is defined by two parameters ϰ and ϱ reflecting trigonal point symmetry C3 V  of each iron site. These parameters are determined by a least squares fit of the experimental Mössbauer spectrum of reduced ferredoxin at 4.2 K and H  ext  = 2 T. In correspondence with the theory, ϰ and ϱ have been proved to be independent of H  ext . Despite neglecting small deviations from T d  and C3 V  point symmetry of the center of the cluster and the iron sites, respectively, theory and experiments are in reasonable good agreement.

Cluster Orbital Theory Based on Mössbauer Effect Investigations of the (Iron) 4 -Sulfur Clusters of Clostridium pasteurianum Ferredoxin