Mössbauer Spectrometry

Mössbauer spectrometry gives electronic, magnetic, and structural information from within materials. A Mössbauer spectrum is an intensity of γ-ray absorption versus energy for a specific resonant nucleus such as ^(57)Fe or ^(119)Sn. For one nucleus to emit a γ-ray and a second nucleus to absorb it with efficiency, both nuclei must be embedded in solids, a phenomenon known as the “Mössbauer effect.” Mössbauer spectrometry looks at materials from the “inside out,” where “inside” refers to the resonant nucleus. Mössbauer spectra give quantitative information on “hyperfine interactions,” which are small energies from the interaction between the nucleus and its neighboring electrons. The three hyperfine interactions originate from the electron density at the nucleus (the isomer shift), the gradient of the electric field (the nuclear quadrupole splitting), and the unpaired electron density at the nucleus (the hyperfine magnetic field). Over the years, methods have been refined for using these three hyperfine interactions to determine valence and spin at the resonant atom. Even when the hyperfine interactions are not easily interpreted, they can often be used reliably as “fingerprints” to identify the different local chemical environments of the resonant atom, usually with a good estimate of their fractional abundances. Mössbauer spectrometry is useful for quantitative phase analyses or determinations of the concentrations of resonant element in different phases, even when the phases are nanostructured or amorphous. Most Mössbauer spectra are acquired with simple laboratory equipment and a radioisotope source, but the recent development of synchrotron instrumentation now allow for measurements on small 10 µm samples, which may be exposed to extreme environments of pressure and temperature. Other capabilities include measurements of the vibrational spectra of the resonant atoms, and coherent scattering and diffraction of nuclear radiation. This article is not a review of the field, but an instructional reference that explains principles and practices, and gives the working materials scientist a basis for evaluating whether or not Mössbauer spectrometry may be useful for a research problem. A few representative materials studies are presented

Elucidating the structural composition of a Fe-N-C catalyst by nuclear and electron resonance techniques

Fe–N–C catalysts are very promising materials for fuel cells and metal–air batteries. This work gives fundamental insights into the structural composition of an Fe–N–C catalyst and highlights the importance of an in‐depth characterization. By nuclear‐ and electron‐resonance techniques, we are able to show that even after mild pyrolysis and acid leaching, the catalyst contains considerable fractions of α‐iron and, surprisingly, iron oxide. Our work makes it questionable to what extent FeN4 sites can be present in Fe–N–C catalysts prepared by pyrolysis at 900 °C and above. The simulation of the iron partial density of phonon states enables the identification of three FeN4 species in our catalyst, one of them comprising a sixfold coordination with end‐on bonded oxygen as one of the axial ligands

Iron environment non-equivalence in both octahedral and tetrahedral sites in NiFe2O4 nanoparticles: study using Mössbauer spectroscopy with a high velocity resolution

Mössbauer spectrum of NiFe2O4 nanoparticles was measured at room temperature in 4096 channels. This spectrum was fitted using various models, consisting of different numbers of magnetic sextets from two to twelve. Non-equivalence of the 57Fe microenvironments due to various probabilities of different Ni2+ numbers surrounding the octahedral and tetrahedral sites was evaluated and at least 5 different microenvironments were shown for both sites. The fit of the Mössbauer spectrum of NiFe 2O4 nanoparticles using ten sextets showed some similarities in the histograms of relative areas of sextets and calculated probabilities of different Ni2+ numbers in local microenvironments. © 2012 American Institute of Physics

Study of olivines from Omolon and Seymchan meteorites using X-ray diffraction and Mössbauer spectroscopy with a high velocity resolution

Study of olivine from Omolon and Seymchan meteorites was performed using X-ray diffraction and Mössbauer spectroscopy with a high velocity resolution. X-ray diffraction patterns were measured at room temperature while Mössbauer spectra were measured at 295 and 90 K. The orthorhombic crystal lattice parameters were evaluated for olivine from Omolon and Seymchan. These parameters appeared to be different for olivines from both meteorites. Mössbauer spectral components related to 57Fe in crystallographically non-equivalent sites M1 and M2 in both olivines were determined and its Mössbauer hyperfine parameters were evaluated. Some differences in the tendencies of temperature dependence of spectral parameters and small variations of 57Fe quadrupole splitting in both M1 and M2 sites of olivines from Omolon and Seymchan were found. On the basis of Mössbauer parameters and chemical data, the temperatures of equilibrium cation distribution were evaluated for both olivines. © 2012 American Institute of Physics

Evaluation of the Debye temperature for iron cores in human liver ferritin and its pharmaceutical analogue Ferrum Lek using Mossbauer spectroscopy

An iron polymaltose complex Ferrum Lek used as antianemic drug and considered as a ferritin analogue and human liver ferritin were investigated in the temperature range from 295K to 90K by means of 57Fe Mossbauer spectroscopy with a high velocity resolution i.e. in 4096 channels. The Debye temperatures equal to 502K for Ferrum Lek and to 461K for human liver ferritin were determined from the temperature dependence of the center shift obtained using two different fitting procedures.Comment: 13 pages, 5 figure

On the calculation of Mössbauer isomer shift

A quantum chemical computational scheme for the calculation of isomer shift in Mössbauer spectroscopy is suggested. Within the described scheme, the isomer shift is treated as a derivative of the total electronic energy with respect to the radius of a finite nucleus. The explicit use of a finite nucleus model in the calculations enables one to incorporate straightforwardly the effects of relativity and electron correlation. The results of benchmark calculations carried out for several iron complexes as well as for a number of atoms and atomic ions are presented and compared with the available experimental and theoretical data.

In situ high-temperature Mössbauer spectroscopic study of carbon nanotube-Fe-Al2O3 nanocomposite powder

The oxidation of a carbon nanotube–Fe–Al2O3 nanocomposite powder was investigated using notably thermogravimetric analysis, room temperature transmission and emission Mössbauer spectroscopy and, for the first time, in situ high-temperature transmission Mössbauer spectroscopy. The first weight gain (150–300 °C) was attributed to the oxidation into hematite of the α-Fe and Fe3C particles located at the surface and in the open porosity of the alumina grains. The 25 nm hematite particles are superparamagnetic at 250 °C or above. A weight loss (300–540 °C) corresponds to the oxidation of carbon nanotubes and graphene layers surrounding the nanoparticles. The graphene layers surrounding γ-Fe–C particles are progressively oxidized and a very thin hematite layer is formed at the surface of the particles, preventing their complete oxidation while helping to retain the face-centered cubic structure. Finally, two weight gains (670 and 1120 °C) correspond to the oxidation of the intragranular α-Fe particles and the γ-Fe–C particles

Synchrotron Mössbauer spectroscopic study of ferropericlase at high pressures and temperatures

The electronic spin state of Fe^(2+) in ferropericlase, (Mg_(0.75)Fe_(0.25))O, transitions from a high-spin (spin unpaired) to low-spin (spin paired) state within the Earth’s mid-lower mantle region. To better understand the local electronic environment of high-spin Fe^(2+) ions in ferropericlase near the transition, we obtained synchrotron Mössbauer spectra (SMS) of (Mg_(0.75),Fe_(0.25))O in externally heated and laser-heated diamond anvil cells at relevant high pressures and temperatures. Results show that the quadrupole splitting (QS) of the dominant high-spin Fe^(2+) site decreases with increasing temperature at static high pressure. The QS values at constant pressure are fitted to a temperature-dependent Boltzmann distribution model, which permits estimation of the crystal-field splitting energy (Δ_3) between the d_(xy_ and d_(xz) or d_(zy) orbitals of the t_(2g) states in a distorted octahedral Fe^(2+) site. The derived Δ_3 increases from approximately 36 meV at 1 GPa to 95 meV at 40 GPa, revealing that both high pressure and high temperature have significant effects on the 3d electronic shells of Fe^(2+) in ferropericlase. The SMS spectra collected from the laser-heated diamond cells within the time window of 146 ns also indicate that QS significantly decreases at very high temperatures. A larger splitting of the energy levels at high temperatures and pressures should broaden the spin crossover in ferropericlase because the degeneracy of energy levels is partially lifted. Our results provide information on the hyperfine parameters and crystal-field splitting energy of high-spin Fe^(2+) in ferropericlase at high pressures and temperatures, relevant to the electronic structure of iron in oxides in the deep lower mantle