Abstract
The isomer shift of the Mössbauer resonance is a rather unique quantity that cannot be obtained by any of the other techniques used for measuring hyperfine interactions in solids, such as NMR or perturbed angular correlations (TDPAC). It shifts the resonance pattern as a whole without affecting the magnetic dipole and electric quadrupole hyperfine splittings. Methods that measure only these hyperfine splittings are insensitive to the isomer shift. The magnitude of the observed shift is proportional to the product of a nuclear parameter, the change Δ⟨r 2⟩ of the nuclear radius that goes along with the Mössbauer transition, and to an electronic property of the material, the electron density ρ(0) at the Mössbauer nucleus or, more precisely, to the difference Δρ(0) of the electron densities at the Mössbauer nuclei in the materials of which the source and the absorber are made. The electron density at the nucleus is due to s-electrons and, to a lesser extent and mainly in heavy nuclei, to relativistic p1 ∕ 2-electrons. All the other electrons have a vanishing density inside the nucleus and do not contribute. Thus, to a very good accuracy, the Mössbauer isomer shift enables one to obtain information on the s-electron density at the Mössbauer nuclei in solids.
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Notes
- 1.
The energy, indeed, becomes bigger for 57Fe because the nucleus in this case is smaller in the excited state than in the groundstate.
- 2.
Electron densities are often given in atomic units (a.u.). An atomic unit for the electron density is the number of electrons found within a volume of a 0 3, where a 0 = 0. 0529 nm is Bohr’s radius.
- 3.
The rarer case of evaluating Δ⟨r 2⟩ in terms of nuclear models is described elsewhere in this volume [13].
- 4.
The source matrix should be cubic and non-magnetic to yield a single line, and it should not show radiochemical effects of the nuclear decay, which is best guaranteed by a metallic matrix. For 57Fe Mössbauer spectroscopy, it has become customary to use metallic rhodium as the source matrix.
- 5.
Details can be found on the Wien2k web site (www.wien2k.at).
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Wagner, F.E., Stievano, L. (2012). Isomer Shifts in Solid State Chemistry. In: Kalvius, M., Kienle, P. (eds) The Rudolf Mössbauer Story. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-17952-5_10
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