Mössbauer spectroscopy is a spectroscopic technique based on the Mössbauer effect. This effect, discovered by Rudolf Mössbauer (sometimes written "Moessbauer", German: "Mößbauer") in 1958, consists of the nearly recoil-free emission and absorption of nuclear gamma rays in solids. The consequent nuclear spectroscopy method is exquisitely sensitive to small changes in the chemical environment of certain nuclei. Typically, three types of nuclear interactions may be observed: the isomer shift due to differences in nearby electron densities (also called the chemical shift in older literature), quadrupole splitting due to atomic-scale electric field gradients; and magnetic splitting due to non-nuclear magnetic fields. Due to the high energy and extremely narrow line widths of nuclear gamma rays, Mössbauer spectroscopy is a highly sensitive technique in terms of energy (and hence frequency) resolution, capable of detecting changes of just a few parts in 1011.
Basic principle
Just as a gun recoils when a bullet is fired, conservation of momentum requires a nucleus (such as in a gas) to recoil during the emission or absorption of a gamma ray. If a nucleus at rest emits a gamma ray, the energy of the gamma ray is slightly less than the natural energy of the transition, but in order for a nucleus at rest to absorb a gamma ray, the gamma ray's energy must be slightly greater than the natural energy because in both cases energy is lost to recoil. This means that nuclear resonance (emission and absorption of the same gamma ray by identical nuclei) is unobservable with free nuclei because the shift in energy is too great, and the emission and absorption spectra have no significant overlap. Nuclei in a solid crystal, however, are not free to recoil because they are bound in place in the crystal lattice. When a nucleus in a solid emits or absorbs a gamma ray, some energy can still be lost as recoil energy, but in this case, it always occurs in discrete packets called phonons (quantized vibrations of the crystal lattice). Any whole number of phonons can be emitted, including zero, which is known as a "recoil-free" event. In this case, the conservation of momentum is satisfied by the momentum of the crystal as a whole, so practically no energy is lost. Mössbauer found that a significant fraction of emission and absorption events will be recoil-free, which is quantified using the Lamb–Mössbauer factor. This fact is what makes Mössbauer spectroscopy possible, because it means that gamma rays emitted by one nucleus can be resonantly absorbed by a sample containing nuclei of the same isotope, and this absorption can be measured. The recoil fraction of the Mössbauer absorption is analyzed by nuclear resonance vibrational spectroscopy.
Typical method In its most common form, Mössbauer absorption spectroscopy, a solid sample is exposed to a beam of gamma radiation, and a detector measures the intensity of the beam transmitted through the sample. The atoms in the source emitting the gamma rays must be of the same isotope as the atoms in the sample absorbing them. If the emitting and absorbing nuclei were in identical chemical environments, the nuclear transition energies would be exactly equal and resonant absorption would be observed with both materials at rest. The difference in chemical environments, however, causes the nuclear energy levels to shift in a few different ways, as described below. Although these energy shifts are tiny (often less than a micro-electronvolt), the extremely narrow spectral linewidths of gamma rays for some radionuclides make the small energy shifts correspond to large changes in absorbance. To bring the two nuclei back into resonance, it is necessary to change the energy of the gamma ray slightly, and in practice, this is always done using the Doppler shift. During Mössbauer absorption spectroscopy, the source is accelerated through a range of velocities using a linear motor to produce a Doppler effect and scan the gamma-ray energy through a given range. A typical range of velocities for 57Fe, for example, can be ±11 mm/s (1 mm/s = 48.075 neV). In the resulting spectra, gamma ray intensity is plotted as a function of the source velocity. At velocities corresponding to the resonant energy levels of the sample, a fraction of the gamma rays are absorbed, resulting in a drop in the measured intensity and a corresponding dip in the spectrum. The number, positions, and intensities of the dips (also called peaks; dips in transmittance are peaks in absorbance) provide information about the chemical environment of the absorbing nuclei and can be used to characterize the sample.
Selecting a suitable source Suitable gamma-ray sources consist of a radioactive parent that decays to the desired isotope. For example, the source for 57Fe consists of 57Co, which decays by electron capture to an excited state of 57Fe, which in turn decays to a ground state via a series of gamma-ray emissions that include the one exhibiting the Mössbauer effect. The radioactive cobalt is prepared on a foil, often of rhodium. Ideally the parent isotope will have a convenient half-life. Also, the gamma-ray energy should be relatively low, otherwise the system will have a low recoil-free fraction resulting in a poor signal-to-noise ratio and requiring long collection times. The periodic table below indicates those elements having an isotope suitable for Mössbauer spectroscopy. Of these, 57Fe is by far the most common element studied using the technique, although 129I, 119Sn, and 121Sb are also frequently studied.
Analysis of Mössbauer spectra As described above, Mössbauer spectroscopy has an extremely fine energy resolution and can detect even subtle changes in the nuclear environment of the relevant atoms. Typically, there are three types of nuclear interactions that are observed: isomeric shift, quadrupole splitting, and hyperfine magnetic splitting.
Isomer shift
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