Mossbauer isotope

Not all nuclear transitions of this kind produce a detectable y-ray for a certain portion, the energy is dissipated by internal conversion to an electron of the K-shell which is ejected as a so-called conversion electron. For some Mossbauer isotopes, the total internal conversion coefficient ax is rather high, as for the 14.4 keV transition of Fe (ax = 8.17). ax is defined as the ratio of the number of conversion electrons to the number of y-photons. 

Mossbauer spectra are usually recorded in transmission geometry, whereby the sample, representing the absorber, contains the stable Mossbauer isotope, i.e., it is not radioactive. A scheme of a typical spectrometer setup is depicted in Fig. 3.1. The radioactive Mossbauer source is attached to the electro-mechanical velocity transducer, or Mossbauer drive, which is moved in a controlled manner for the modulation of the emitted y-radiation by the Doppler effect. The Mossbauer drive is powered by the electronic drive control unit according to a reference voltage (Fr), provided by the digital function generator. Most Mossbauer spectrometers are operated in constant-acceleration mode, in which the drive velocity is linearly swept up and down, either in a saw-tooth or in a triangular mode. In either case. 

Mossbauer nuclei per square centimetre, the Debye-Waller factor/a of the absorber material, and the resonance cross-section Gq of the Mossbauer isotope. For a multiline spectrum, the result must be split into separate values for each line, which are obtained by weighting t with the relative transition probability of each line. 

Similar dependencies and trends are observed for other Mossbauer isotopes, for which more information is found in Chap. 7. It should be pointed out again that the nuclear parameter l RIR is negative for Fe in contrast to many other nuclei. The sign of the isomer shift correlations is inverted for nuclei with A/ // > 0. 

Taken from Mossbauer Effect Data Center (MEDC), Prof John Stevens, University of North Carolina, Asheville, NC, USA, September 2009 for a full list of the nuclear properties for all known Mossbauer isotopes see the MEDC web address http //orgs. unca.edu/medc/Resources.html, or the corresponding pdf file in the CD-ROM of this book An older report [46] states -720 mb the value reported by MEDC is -789 mb... 

The experimentally observed quadrupole splitting AEq for Fe in inorganic compounds, metals, and solids reaches from 0 to more than 6 mm s [30, 32]. The range of AEq for other Mossbauer isotopes may be completely different because of the different nuclear quadrupole moment Q of the respective Mossbauer nucleus, and also because the EFG values may be intrinsically different due to markedly different radial distributions of the atomic orbitals (vide infra). As Q is constant for a given isotope, variations in the quadrupole coupling constants eQV can only arise from... 

Mossbauer resonance of Zn to study the influence of the gravitational field on electromagnetic radiation. A Ga ZnO source (4.2 K) was used at a distance of 1 m from an enriched ZnO absorber (4.2 K). A red shift of the photons by about 5% of the width of the resonance line was observed. The corresponding shift with Fe as Mossbauer isotope would be only 0.01%. The result is in accordance with Einstein s equivalence principle. Further gravitational red shift experiments using the 93.3 keV Mossbauer resonance of Zn were performed later employing a superconducting quantum interference device-based displacement sensor to detect the tiny Doppler motion of the source [66, 67]. 

The parent nuclei of the hafnium Mossbauer isotopes can be produced by the following reactions ... 

The isomer shifts in hafnium Mossbauer isotopes usually are of the order of some percent of the line width. Boolchand et al. [168] observed a relatively large isomer shift of -1-0.19 0.06 mm s between cyclopentadienyl hafnium dichloride (Hf(Cp)2Cl2) and Hf metal. From a comparison with Os(Cp)2 and Os-metal, a value of 5 r ) ( Hf) = —0.37 10 fm has been derived, which implies a shrinking of the nuclear radius in the excited 2 state. Figure 7.37 shows some typical spectra for Hf in various hafnium compounds (from [168]). 

Kaindl et al. [186] have plotted the isomer shift results for metallic hosts versus the number of outer electrons of the 3d, Ad, and 5d metals and found the transition energy to decrease when proceeding from a to a Ad and further to a 3d host metal in the same column of the periodic table. This systematic behavior is similar to that observed for isomer shifts of y-rays of Fe(14.4 keV) [193], Ru(90 keV), Pm (77 keV), and lr(73 keV) [194]. The changes of A(r ) = (r )e — (r )g for these Mossbauer isotopes are all reasonably well established. Kaindl et al. [186] have used these numbers to estimate, with certain assumptions, the A(r ) value for Ta (6.2 keV) and found a mean value of A(r ) = —5 10 fin with some 50% as an upper limit of error. The negative sign of A(r ) is in agreement with the observed variation of the isomer shift of LiTaOs, NaTaOs, and KTaOs, as well as with the isomer shift found for TaC [186]. 

Determination of Nuclear Parameters of Osmium Mossbauer Isotopes... 

Mossbauer measurements with determination of the electric quadrupole moments have been reported in [253, 254,259]. Wagner et al. [254] measured the quadrupole hyperfine interaction in OSO2 and OSP2 of the Mossbauer isotopes The ratios of the quadrupole moments of the 4 = 72 states in the even osmium isotopes and of the 4 = 5/2 (69.6 keV) and 4 = 3/2 states in Os were deduced very accurately. In Table 7.8, the experimental results [254] are given, from which the following ratios can be calculated ... 

There are two iridium isotopes, ir and Ir, suitable for Mossbauer spectroscopy. Each of them possesses two nuclear transitions with which nuclear resonance absorption has been observed. Figure 7.58 (from [266]) shows the (simplified) nuclear decay schemes for both iridium Mossbauer isotopes the Mossbauer transitions are marked therein with bold arrows. The relevant nuclear data known to date for the four Mossbauer transitions are collected in Table 7.1 at the end of the book. 

The lr Mossbauer experiments are usually carried out in transmission geometry with both source and absorber kept at liquid helium temperature and a Ge(Li) diode or a 3 mm Nal(Tl) crystal used to detect the 73 keV y-rays. The absorbers typically contain 50-500 mg cm of natural iridium, which contains 62.7% of the Mossbauer isotope lr. The isomer shifts are generally given with respect to iridium metal (the isomer shift between Os/Os and Ir metal is (0.540 0.004) mm s at 4.2 K ([268]). 

Fe2fr2(CO)i2 t3- Au(PPh3) ] [Fe2lr2(CO)i2 tt3-Au(PPh3) ], which has a trigonal bipyramidal core consisting of five atoms of three different Mossbauer isotopes, was studied by Ir, Au and Fe Mossbauer spectroscopy. The nature and the chemical character of the atoms located at the different sites are discussed with respect to their Mossbauer spectra... 

In 1971, Walcher [326] succeeded in observing a resonance effect of about 0.6% in as a function of the Doppler velocity using a TI2O3 source and an enriched (81% ° Hg) HgO absorber at 4.2 K. The half-width turned out to be Fexp = 76 (10) mm s corresponding to a lower limit of the half-life of fi/2 > 0.1 ns. It is clear that the properties of the ° Hg Mossbauer isotope do not render it an interesting isotope from a chemical point of view. 

By far the most utilized Mossbauer isotope is Fe, particularly in (bio)inorganic chemistry. Most iron compounds are found in the oxidation states iron(ll) and iron (III), either with low-spin or high-spin electron configuration. The literature on the application of Fe Mossbauer spectroscopy in this field of research has been reviewed in several textbooks, which are referenced in Chap. 1. The present chapter is intended as a survey of the Mossbauer studies on iron compounds with less common, nevertheless increasingly interesting, valence and spin states. 

The use of synchrotron radiation overcomes some of the limitations of the conventional technique. The high brilliance of up to 10 ° photons s mm mrad /0.1% bandwidth of energy, and the extremely collimated synchrotron beam lead to a large flux of photons through a very small cross section (0.1-1 mm ). This allows measurements with samples of small volume if isotopi-cally enriched (with the relevant Mossbauer isotope, e.g., Fe). Measurements that were described earlier [4] and that require a polarized Mossbauer source now become experimentally more feasible by making use of the polarization of the synchrotron radiation. Additionally, the energy can be tuned over a wide range. This facilitates measurements with those Mossbauer nuclei for which conventional sources are available but with life times that are too short for most experimental purposes, e.g., 99 min for Co —> Ni and 78 h for Ga —> Zn. 

Nuclear absorption of incident X-rays (from the synchrotron beam) occurs elastically, provided their energy, y, coincides precisely with the energy of the nuclear transition, Eq, of the Mossbauer isotope (elastic or zero-phonon peak at = E m Fig. 9.34). Nuclear absorption may also proceed inelasticaUy, by creation or annihilation of a phonon. This process causes inelastic sidebands in the energy spectrum around the central elastic peak (Fig. 9.34) and is termed nuclear inelastic scattering (NIS). 

Complementary to other methods that constimte a basis for the investigation of molecular dynamics (Raman scattering, infrared absorption, and neutron scattering), NIS is a site- and isotope-selective technique. It yields the partial density of vibrational states (PDOS). The word partial refers to the selection of molecular vibrations in which the Mossbauer isotope takes part. The first NIS measurements were performed in 1995 to constitute the method and to investigate the PDOS of... 

Potential Mossbauer isotopes for nuclear resonance scattering, which are within the spectral reach of synchrotron radiation sources, are summarized in Table 9.5 [118-120], and the synchrotron radiation sources which provide dedicated beam lines for specific Mossbauer isotopes are listed in Table 9.6 (adopted from [85]). 

Table 9.5 Potential Mossbauer isotopes for nuclear resonance scattering, which are within the spectral reach of currently available synchrotron radiation sources...

Core electrons are highly relativistic and DFT methods may show systematic errors in calculating the charge density at the nucleus because of the inherent approximations. Fortunately, this does not hamper practical calculations of isomer shifts of unknown compounds, because only differences of li//(o)P are involved. In practice, the reliability of the results depends more on the number of compounds used for calibration and how wide the spread of their isomer shift values was. The isomer shift scale for several Mossbauer isotopes has been calibrated by this approach, among which are Au [1], Sn [4], and Fe [5-9]. For details on practical calculation of Mossbauer isomer shifts, see Chap. 5. 

Mossbauer Measurements. Co-Mo catalysts cannot be studied directly in absorption experiments since neither cobalt nor molybdenum has suitable Mossbauer isotopes. However, by doping with 57Co the catalysts can be studied by carrying out Mossbauer emission spectroscopy (MES) experiments. In this case information about the cobalt atoms is obtained by studying the 57Fe atoms produced by the decay of 57Co. The possibilities and limitations on the use of the MES technique for the study of Co-Mo catalysts have recently been discussed (8., 25.). 

Next to Fe, Sn is the second best Mossbauer isotope, in the sense that the y-ray energy, Mossbauer lifetime, and parent lifetime are all satisfactory. To use isomer shift measurements eflFectively, one must know the relative change in nuclear radius (8R/R). In the case of Sn, the correct value for this quantity was indefinite, both as to sign and magnitude. 

Dr. Flinn Antimony would be exciting to many chemists. Antimony-121 is the Mossbauer isotope of antimony. The first work was done at Wayne State University, and recently there has been a good deal of work by Ruby and others at Argonne which should be appearing shortly. It seems that antimony is similar to tin in its relationship between isomer shift and the various compounds. It is better than tin in that the isomer shift is about five times larger so that precise measurements are possible. Thanks to Ruby s work, the changes with chemical environment are well understood. The AR/R situation is clear cut, but there are some difficulties in preparing a satisfactory source. The parent is tin-121 which is m de by neutron capture by tin-120. The reaction has one of the smallest cross-sections in existence—one can place the tin in a reactor for a year and not produce much even then. However, when a source is obtained, you are in business for a while. Its half-life is 25 years. 

Dr. Hafemeister If you pulse the accelerator and remove all the short-lived activity and if the Mossbauer isotope remains awhile, tlien you can throw away the coincidence requirement. 

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