Nuclear transitions, Mossbauer spectroscopy

Up to the present time, the Mossbauer effect has been observed with nearly 100 nuclear transitions in about 80 nuclides distributed over 43 elements (cf. Fig. 1.1). Of course, as with many other spectroscopic methods, not all of these transitions are suitable for actual studies, for reasons which we shall discuss later. Nearly 20 elements have proved to be suitable for practical applications. It is the purpose of the present book to deal only with Mossbauer active transition elements (Fe, Ni, Zn, Tc, Ru, Hf, Ta, W, (Re), Os, Ir, Pt, Au, Hg). A great deal of space will be devoted to the spectroscopy of Fe, which is by far the most extensively used Mossbauer nuclide of all. We will not discuss the many thousands of reports on Fe... 

The ratio F/Eq of width F and the mean energy of the transition Eo defines the precision necessary in nuclear y-absorption for tuning emission and absorption into resonance. Lifetimes of excited nuclear states suitable for Mossbauer spectroscopy range from 10 s to s. Lifetimes longer than 10 s produce too... 

In Table 7.1 at the end of the book), nuclear data are collected for those Mdssbauer transitions of transition metal nuclides that are used in Mossbauer spectroscopy. The symbols used in this table have the following meaning ... 

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. 

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. 

It is a matter of historical interest that Mossbauer spectroscopy has its deepest root in the 129.4 keV transition line of lr, for which R.L. Mossbauer established recoilless nuclear resonance absorption for the first time while he was working on his thesis under Prof. Maier-Leibnitz at Heidelberg [267]. But this nuclear transition is, by far, not the easiest one among the four iridium Mossbauer transitions to use for solid-state applications the 129 keV excited state is rather short-lived (fi/2 = 90 ps) and consequently the line width is very broad. The 73 keV transition line of lr with the lowest transition energy and the narrowest natural line width (0.60 mm s ) fulfills best the practical requirements and therefore is, of all four iridium transitions, most often (in about 90% of all reports published on Ir Mossbauer spectroscopy) used in studying electronic stractures, bond properties, and magnetism. 

The nuclear transitions are very sensitive to the local environment of the atom, and Mossbauer spectroscopy is a sensitive probe of the different environments an atom occupies in a solid material. By analyzing the chemical shifts and quadrupole splitting in Mossbauer spectra of samples containing Mossbauer-ac-tive nuclei, information on the state of oxidation and the local structure can be obtained. Only a few nuclei can be used for this purpose, so this method has limited but powerful applications. 

The recoilless nuclear resonance absorption of y-radiation (Mossbauer effect) has been verified for more than 40 elements, but only some 15 of them are suitable for practical applications [33, 34]. The limiting factors are the lifetime and the energy of the nuclear excited state involved in the Mossbauer transition. The lifetime determines the spectral line width, which should not exceed the hyperfine interaction energies to be observed. The transition energy of the y-quanta determines the recoil energy and thus the resonance effect [34]. 57Fe is by far the most suited and thus the most widely studied Mossbauer-active nuclide, and 57Fe Mossbauer spectroscopy has become a standard technique for the characterisation of SCO compounds of iron. 

About twenty years ago we reported on the di-isothiocyanato iron(II) complex of the tetradentate ligand tpa (tris(2-pyridylmethyl)amine) [7] (6). It was shown that this complex exhibits the spin crossover phenomenon with a critical temperature Tm of about 170 K. Several different solvated phases of the same system have since been characterized by Chansou et al. [8]. The unsolvated phase which can be isolated from an aqueous solution has been investigated by nuclear forward scattering (NFS), nuclear inelastic scattering (NIS) [9], extended x-ray absorption fine structure (EXAFS) spectroscopy, conventional Mossbauer spectroscopy, and by measurements of the magnetic susceptibility (SQUID) [10-13]. The various measurements consistently show that the transition is complete and abrupt and it exhibits a hysteresis loop between 102 and 110 K. 

Until the discovery of the Mossbauer effect, the possibility of directly observing nuclear y-ray transitions between individual nuclear magnetic substates seemed remote because of the small energy differences involved however, the extremely high energy resolution of Mossbauer spectroscopy has made it possible to resolve these transitions directly in some isotopes, and it is this feature that is so valuable for investigating... 

Mossbauer spectroscopy is based on transition between energy levels of nuclei with different values of the nuclear spin quantum number /. When a nucleus emits a y-ray, the energy of the emitted radiation is lowered by the recoil of the nucleus. Conversely, the energy needed for absorption is higher than that needed for transition, because the absorbing nucleus absorbs energy in the recoil process. For nuclei tightly bound in solids, however, the effective mass of the emitter and... 

Spectroscopy produces spectra which arise as a result of interaction of electromagnetic radiation with matter. The type of interaction (electronic or nuclear transition, molecular vibration or electron loss) depends upon the wavelength of the radiation (Tab. 7.1). The most widely applied techniques are infrared (IR), Mossbauer, ultraviolet-visible (UV-Vis), and in recent years, various forms ofX-ray absorption fine structure (XAFS) spectroscopy which probe the local structure of the elements. Less widely used techniques are Raman spectroscopy. X-ray photoelectron spectroscopy (XPS), secondary ion imaging mass spectroscopy (SIMS), Auger electron spectroscopy (AES), electron spin resonance (ESR) and nuclear magnetic resonance (NMR) spectroscopy. 

Mossbauer spectroscopy provides measurements of the resonant absorption of y-rays by nuclear transitions from a ground state to an excited state. Like other nuclear techniques, it is based on a phenomenon that is specific to a given isotope and for which no interference from other isotopes is possible. 

In conventional Mossbauer spectroscopy, X-rays with energies corresponding to nuclear transitions (5-150keV) can be produced only by use of radioactive sources containing a parent isotope of the absorbing nucleus in an appropriate excited state from which it decays into the ground state with emission of a y-quantum. For spectroscopic applications, the y-radiation must be variable. The chemical perturbations... 

Figure 14 shows three Fe case studies of the time behavior of the photons reemitted in the forward direction and a comparison with the typical spectra obtained in Mossbauer spectroscopy. Figure 14a corresponds to the case for which there is no hyperfine interaction. The nuclear levels are not split, and only one transition between ground and excited state is possible. In that case, the Mossbauer spectrum shows a single-absorption line and contains only y-quanta of equal energy. In the presence of an electric field gradient (Fig. 14b), the splitting of the excited state is... 

Fig. 2.44. Mossbauer spectroscopy (a) nuclear transitions giving rise to the Mossbauer effect in Fe (b) principles involved in the Mossbauer spectrometer (c) Mdssbauer resonant absorption of iron in different crystal environments and the resulting spectral types. (After Vaughan and Craig, 1978 reproduced with the publisher s permission).

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