Spin fluctuations of paramagnetic iron centers in proteins and model complexes: Mössbauer and EPR results

• Published in: The Journal of chemical physics 1987-11, Vol.87 (9), p.5077-5091
• Main Authors: SCHULZ, C. E, NYMAN, P, DEBRUNNER, P. G
• Format: Article
• Language: English
• Subjects: Biological and medical sciences; Fundamental and applied biological sciences. Psychology; Molecular biophysics; Spectroscopy : techniques and spectras
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.453675

We have analyzed the Mössbauer spectra of several iron proteins in the regime of intermediate fluctuation rates of the magnetic hyperfine interaction using the dynamic line shape model of Clauser and Blume. All Mössbauer data were recorded in applied fields so that the electron Zeeman interaction is much larger than the hyperfine splittings. We modeled the transitions between the eigenstates of the electronic spin Hamiltonian by an effective spin–phonon coupling V(1)=V0∑′i,j=x,y,zSi Sj and described the phonons in the Debye approximation. With V0 as the only adjustable parameter the model reproduced the major temperature dependence of the spectral shapes for spins from S=1 to S=5/2. We found V0 to lie in the narrow range 3 K ≤V0/k≤19 K, which is of the order of the zero-field splittings, but does not correlate with it. The smallest values of V0 were observed in the four-coordinate iron–sulfur proteins. Refinements and implications of the model are discussed.