Mossbauer magnetic hyperfine interactions

Pure nuclear magnetic hyperfine interaction without electric quadrupole interaction is rarely encountered in chemical applications of the Mossbauer effect. Metallic iron is an exception. Quite frequently, a nuclear state is perturbed simultaneously by... 

Fig. 4.13 Combined magnetic hyperfine interaction for Fe with strong electric quadrupole interaction. Top left, electric quadrupole splitting of the ground (g) and excited state (e). Top right first-order perturbation by magnetic dipole interaction arising from a weak field along the main component > 0 of the EFG fq = 0). Bottom the resultant Mossbauer spectrum is shown for a single-crystal type measurement with B fixed perpendicular to the y-rays and B oriented along...

The underlying physics and analysis of Mossbauer spectra have been explained in detail in Chap. 4. In that chapter, the principles of how a spectrum is parameterized in terms of spin-Hamiltonian (SH) parameters and the physical origin of these SH parameters have been clarified. Many Mossbauer studies, mainly for Fe, have been performed and there is a large body of experimental data concerning electric-and magnetic-hyperfine interactions that is accessible through the Mossbauer Effect Database. 

The third prominent interaction in iron Mossbauer spectroscopy is the magnetic hyperfine interaction of the Fe nucleus with a local magnetic field. As explained in detail in Chap. 4, it can be probed by performing the Mossbauer experiment in the presence of an applied external magnetic field. 

Fig. 7.83 Mossbauer transmission spectra of Au/Fe multilayer systems with varying Au-layer thickness, measured at 16 K and fitted by a four-component model, including magnetic hyperfine interaction at the Au layer atoms (from [437])...

There have been two additional experiments which verified this basic picture of the nuclear hyperfine interaction in hemins. Johnson (78) increased the spin-lattice relaxation time by performing the Mossbauer experiment under field and temperature conditions which provide a large value of H/T. At 1.6 °K and in an applied field of 30 kG, a magnetic hyperfine interaction corresponding to that expected for high spin Fe(III) and for the g-values is measured experimentally. Recently, Lang et al. have found that a portion of hemin chloride dissolved in tetrahydro-furan at 1 mM concentration displays a hyperfine interaction at 4 °K in zero applied magnetic field. Their conclusion is that a portion of the hemin is present in a monomeric form in this solvent, a situation which is not apparent to any extent in water, acetic acid, chloroform, or dimethyl sulfoxide (77) at any concentrations used. 

In order to complete the discussion of magnetic hyperfine interactions in paramagnetic heme proteins as detected by Mossbauer spectroscopy, reference should be made to the work of Champion et al. (58). There the influence of the halides F, Cl, and I on ferric chloroperoxidase was studied. The results presented in this work indicate that halide anions,... 

One less-well-known technique, which has many experimental aspects in common with Mossbauer spectroscopy, deserves special attention at this point, since it gives valuable information about the electric-field gradients and the magnetic hyperfine interactions of radioactive nuclei in solids at ambient conditions and under pressure. In this technique, two y-rays with different energies from two different transitions of an individual nucleus in a radioactive-decay cascade are recorded consecutively. The spatial and temporal perturbation of the emission probability by the hyperfine fields is registered in the corresponding perturbed angular correlation (PAC) spectra. 

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