Mossbauer experiments

The same Ketjen alumina described earlier was used for the Mossbauer experiments. The samples were prepared Identically, with the following exceptions. The extrudate was ground to 20-40 mesh before Impregnation, and 0.5 gram samples were prepared using 2 mCl of Co. The samples were prepared to give 8.9% Ho and 1.2%... 

Sulfiding for the Mossbauer experiments was similar. All conditions were Identical except an 8% H2S/H2 blend was used. Figure... 

A unique situation is encountered if Fe-M6ssbauer spectroscopy is applied for the study of spin-state transitions in iron complexes. The half-life of the excited state of the Fe nucleus involved in the Mossbauer experiment is tj/2 = 0.977 X 10 s which is related to the decay constant k by tj/2 = ln2/fe. The lifetime t = l//c is therefore = 1.410 x 10 s which value is just at the centre of the range estimated for the spin-state lifetime Tl = I/Zclh- Thus both the situations discussed above are expected to appear under suitable conditions in the Mossbauer spectra. The quantity of importance is here the nuclear Larmor precession frequency co . If the spin-state lifetime Tl = 1/feLH is long relative to the nuclear precession time l/co , i.e. Tl > l/o) , individual and sharp resonance lines for the two spin states are observed. On the other hand, if the spin-state lifetime is short and thus < l/o) , averaged spectra with intermediate values of quadrupole splitting A q and isomer shift 5 are found. For the intermediate case where Tl 1/cl , broadened and asymmetric resonance lines are obtained. These may be the subject of a lineshape analysis that will eventually produce values of rate constants for the dynamic spin-state inter-conversion process. The rate constants extracted from the spectra will be necessarily of the order of 10 -10 s"F... 

The quadrupole interaction operator in a Mossbauer experiment may be expressed as ... 

Resonant y-ray absorption is directly connected with nuclear resonance fluorescence. This is the re-emission of a (second) y-ray from the excited state of the absorber nucleus after resonance absorption. The transition back to the ground state occurs with the same mean lifetime t by the emission of a y-ray in an arbitrary direction, or by energy transfer from the nucleus to the K-shell via internal conversion and the ejection of conversion electrons (see footnote 1). Nuclear resonance fluorescence was the basis for the experiments that finally led to R. L. Mossbauer s discovery of nuclear y-resonance in ir ([1-3] in Chap. 1) and is the basis of Mossbauer experiments with synchrotron radiation which can be used instead of y-radiation from classical sources (see Chap. 9). 

In this chapter, we present the principles of conventional Mossbauer spectrometers with radioactive isotopes as the light source Mossbauer experiments with synchrotron radiation are discussed in Chap. 9 including technical principles. Since complete spectrometers, suitable for virtually all the common isotopes, have been commercially available for many years, we refrain from presenting technical details like electronic circuits. We are concerned here with the functional components of a spectrometer, their interaction and synchronization, the different operation modes and proper tuning of the instrument. We discuss the properties of radioactive y-sources to understand the requirements of an efficient y-counting system, and finally we deal with sample preparation and the optimization of Mossbauer absorbers. For further reading on spectrometers and their technical details, we refer to the review articles [1-3]. 

The emission spectmm of Co, as recorded with an ideal detector with energy-independent efficiency and constant resolution (line width), is shown in Fig. 3.6b. In addition to the expected three y-lines of Fe at 14.4, 122, and 136 keV, there is also a strong X-ray line at 6.4 keV. This is due to an after-effect of K-capture, arising from electron-hole recombination in the K-shell of the atom. The spontaneous transition of an L-electron filling up the hole in the K-shell yields Fe-X X-radiation. However, in a practical Mossbauer experiment, this and other soft X-rays rarely reach the y-detector because of the strong mass absorption in the Mossbauer sample. On the other hand, the sample itself may also emit substantial X-ray fluorescence (XRF) radiation, resulting from photo absorption of y-rays (not shown here). Another X-ray line is expected to appear in the y-spectrum due to XRF of the carrier material of the source. For rhodium metal, which is commonly used as the source matrix for Co, the corresponding line is found at 22 keV. 

Most Mossbauer experiments are currently performed with commercially available radioactive sources. For some applications, however, a so-called source experiment may be useful, in which the sample is labeled with the radioactive parent-isotope of the Mossbauer nucleus such as Co. The y-radiation of the radioactive sample is then analyzed by moving a single-line absorber for Doppler modulation in front of the detector. 

Fig. 3.22 Backscatter MIMOS II spectra collected in eight temperature intervals on the CCT target (magnetite rock) during a simulated overnight Mossbauer experiment on Mars...

Fig. 3.23 Left-. Calculated relationship between the thickness of an alteration rind and/or dust coating on a rock and the amount of 15.0-keV radiation absorbed in the rind/coating for densities of 0.4, 2.4, and 4.0 g cm [57]. The bulk chemical composition of basaltic rock was used in the calculations, and the 15.0 keV energy is approximately the energy of the 14.4 keV y-ray used in the Mossbauer experiment. The stippled area between densities of 2.4 and 4.0 g cm is the region for dry bulk densities of terrestrial andesitic and basaltic rocks [58]. The stippled area between densities of 0.1 and 0.4 g cm approximates the range of densities possible for Martian dust. The density of 0.1 g cm is the density of basaltic dust deposited by air fall in laboratory experiments [59]. Right Measured spectra obtained on layered laboratory samples and the corresponding simulated spectra, from top to bottom 14.4 keV measured (m) 14.4 keV simulated (s) 6.4 keV measured (m) and 6.4 keV simulated (s). All measurements were performed at room temperature. Zero velocity is referenced with respect to metallic iron foil. Simulation was performed using a Monte Carlo-based program (see [56])...

In a conventional Fe Mossbauer experiment with a powder sample, one would observe a so-called quadrupole doublet with two resonance lines of equal intensities. The separation of the lines, as given by (4.36), represents the quadrupole splitting The parameter Afg is of immense importance for chemical applications of the Mossbauer effect. It provides information about bond properties and local symmetry of the iron site. Since the quadrupole interaction does not alter the mean energy of the nuclear ground and excited states, the isomer shift S can also be derived from the spectrum it is given by the shift of the center of the quadrupole spectrum from zero velocity. 

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. 

Most of the Zn Mossbauer experiments so far have been carried out with ZnO as absorber. De Waard and Perlow [54] used polycrystaUine ZnO enriched to 90% in Zn with various pretreatments. They intended to determine (1) the quadrupole splitting in ZnO, (2) the influence of source and absorber preparation on the width and depth of a resonance, (3) the SOD shift, and (4) the influence of pressure on the source. 

Katila et al. have carried out an unusual Mossbauer experiment of fundamental interest [65]. They have made use of the ultrahigh resolution of the 93.3 keV... 

Nuclear resonance absorption for the 136 keV transition has been established by Steiner et al. [174]. The authors used a metal source and an absorber of metallic tantalum to determine the mean lifetime of the 136 keV level from the experimental line width ( 52.5 mm s for zero effective absorber thickness) and found a value of 55 ps. This has been the only report so far on the use of the 136 keV excited state of Ta for Mossbauer experiments. 

With the observed temperature shift data for (dSldT)p and calculated (within the framework of the Debye model) numbers for the temperature shift of SOD and with the known thermal expansion coefficient as well as results from Ta Mossbauer experiments under pressure, the authors [191] were able to evaluate the true temperature dependence of the isomer shift, (dSisIdT) as —33 10 " and —26 10 " mm s degree for Ta and W host metal, respectively. 

The application of Mossbauer spectroscopy in chemistry requires a prior knowledge of the nuclear states and transitions involved. In this section, we shall describe the determination of nuclear parameters by means of Mossbauer experiments with Os nuclei. 

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]). 

The time-dependent, rapid freeze-quench Mossbauer experiments with M. capsulatus (Bath) (51) indicate that decay of the peroxo species proceeds with the concomitant formation of another intermediate, named compound Q. This intermediate, observed in both the M. tri-chosporium OB3b (69, 70) and M. capsulatus (Bath) (51, 71) MMO systems by Mossbauer and optical spectroscopy, decays faster in the presence of substrates. Such behavior indicates that this intermediate is probably on the kinetic reaction pathway for hydroxylation (51, 70). 

The source for the 14.41-keV y radiation used in Mossbauer experiments is indicated by the boldface arrow in Figure 3.26.3 Origin of the isomer shift and quadrupole splitting phenomena are indicated at the right-hand side of the diagram. 

Figure 3.26 Cobalt-57 source of 14.41-keV y radiation used in Mossbauer experiments. Isomer shift and quadrupole splitting characteristics are shown at right. (Adapted from Figure 2.26 of reference 3 and Figure 1 of reference 24.)...

Figure 5.11 A constant velocity Mossbauer experiment reveals the kinetics of the denitridation of an iron nitride in different gases at 525 K. The negative part of the time scale gives the transmission of the most intense peak of the nitride at time zero the gas atmosphere is changed to the desired gas. Denitridation occurs relatively fast in H2, but is retarded by CO, whereas the nitride is stable in an inert gas such as helium (from Hummel etal. [33]).

The in situ Mossbauer experiments were conducted with 90% - Fe enriched 9 1 Ni/Fe oxyhydroxide films which were deposited in the fashion described above onto a gold on Melinex support(12) in a conventional electrochemical cell. Prior to their transfer into the in situ Mossbauer cell, the electrodes were cycled twice between 0 and 0.6 V vs. Hg/HgO,OH" in 1 M KOH. Two such films were used in the actual Mossbauer measurements in order to reduce the counting time. The in situ Mossbauer cell involved in these experiments was previously described. 

Figure 12, in which the calibration constant, k, in mm./sec. channel, is shown as a function of the analyzer address. In this manner the linearity of the velocity scale can be readily determined over the range of Doppler velocities of interest in most iron and tin Mossbauer experiments.]... 

Because the interactions measured in Mossbauer experiments are products of atomic and nuclear factors, experiments on iodine isotopes have yielded values of the change of nuclear radius between the ground state and the excited state, AR/R, quadrupole moment values Q, and magnetic moment values, fi, as well as electric field gradients and internal magnetic fields. 

Such serious deviations from the predictions of electronegativity are not often found in Mossbauer experiments. In particular, Alexsandrov et al. ( ) and others have found a linear relation between 8 and electronegativity for the tin tetrahalides. Since the differences in electronegativity are much larger for the halogens than the alkalies, the difference in ionicity is much more important for the tin tetrahalides than for the alkali iodides. 

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