Mössbauer Spectroscopy
Source: Joshua Wofford,Tamara M. Powers, Department of Chemistry, Texas A&M University
Mössbauer spectroscopy is a bulk characterization technique tha…
1. Preparation of the Sample
- Weigh 100 mg of ferrocene in a delrine Mössbauer cup.
- Add several drops of paratone oil to the sample. Using a spatula, mix the sample and the oil into a uniform paste.
- Freeze the sample in liquid nitrogen.
2. Mounting the Sample
- Fill the sample chamber with He gas.
- Unscrew the sample rod from the instrument and remove the sample rod.
- While mounting the sample, close the sample chamber with a cap and secure with screws.
- Load the Mössbauer cup into the sample holder at the end of the rod.
- Tighten the screw to secure the cup in the sample holder.
- Dust off any ice that forms before freezing the end of the sample rod in liquid nitrogen.
- With He flowing through the sample chamber, unscrew and remove the cap, and insert the sample rod.
- Secure the rod to the instrument with the screws.
- Turn off the He and pull the vacuum on the sample chamber.
- Turn off the vacuum and refill the sample chamber slightly with He to enable thermal exchange between the sample and the cold head of the instrument via the He gas.
3. Data Collection and Workup
- Open the Mössbauer data collection software. Here we use W302 by Science Engineering & Education (SEE) Co.
- The first screen will show the total count of gamma rays hitting the detector at a range of energies. Select the peak that includes the energy value 14.4 keV and 2 keV escape peak.
- Hit the "Send Windows" button. This will send the data to the W302 software (SEE Co).
- Open the W302 program. Select the desired source velocity (0-12 mm/s). Hit the "clear channel" to begin a new data collection.
- After the desired resolution is reached, fit the data with a suitable program. Here we use WMOSS by SEE Co. The fit provides the values for isomer shift and quadrupole splitting (if a doublet is present).
M?ssbauer spectroscopy is a method for evaluating the oxidation state, electronic spin state, and electronic environment of an atom.
The nuclear spin angular momentum of an atom, or nuclear spin for short, describes the discrete energetic states available to a nucleus. The energy levels are affected by the oxidation state, electronic spin state, and ligand environment.
Differences in nuclear energy levels are reflected in the nuclear excitation energy. M?ssbauer spectroscopy takes advantage of this relationship by irradiating a solid sample with gamma rays over a narrow range of energies and comparing the energies absorbed by the sample to known values.
This video will discuss the underlying principles of M?ssbauer spectroscopy, illustrate the procedure for determining the spin state and oxidation state of ferrocene, and introduce a few applications in chemistry.
When a nucleus absorbs or emits a gamma ray, some energy is lost to recoil. Thus, the gamma ray emitted by a relaxing nucleus cannot excite an identical nucleus.
However, a percentage of emission and absorption events in crystal structures have negligible recoil, allowing resonance to occur between identical nuclei in solids. This is called the M?ssbauer effect.
A standard M?ssbauer spectrometer consists of a moving gamma ray source and a sensitive radiation detector. Iron M?ssbauer spectroscopy is performed with a 57Co source, which decays by electron capture to excited 57Fe.
The different chemical environments of the source and sample nuclei result in slightly different energy gaps between the ground and excited states. The source is therefore moved back and forth at various speeds to induce a Doppler shift in the gamma rays.
The radiation detector measures the gamma rays transmitted through the sample. When the received gamma rays are the precise energy needed to excite the sample, resonant absorption can occur between the source and the sample.
A M?ssbauer spectrum typically plots % transmission vs. energy in terms of source velocity.
The isomer shift is the shift in resonance energy relative to the source, and is related to the oxidation state of the atom.
Nuclear energy levels split when the surrounding electric field gradient is non-spherical, resulting in two distinct absorption energies. This interaction, called quadrupole splitting, occurs in asymmetric ligand environments, and at nuclear spins greater than ?.
Quadrupole splitting results in a quadrupole doublet in the M?ssbauer spectrum. In these cases, the isomer shift is halfway between the two peaks and the quadrupole splitting value is the difference between the peaks.
Hyperfine splitting occurs in an internal or external magnetic field. Each nuclear energy level splits into sub-states based on its nuclear spin state. 57Fe has six allowed transitions between those states, resulting in six peaks.
Now that you understand the principles of M?ssbauer spectroscopy, let's go through a procedure for determining the oxidation state and electronic spin state of ferrocene with M?ssbauer spectroscopy.
To begin the procedure, measure 100 mg of ferrocene into a polyoxymethylene M?ssbauer sample cup.
Add to the sample several drops of a cryoprotectant oil composed of a blend of polyisobutylenes. Use a spatula to mix the sample and oil into a uniform paste. Using tweezers, place the filled M?ssbauer cup into a 20 mL scintillation vial and cap it for transportation to the M?ssbauer instrument room.
Once in the instrumentation room, freeze the sample in liquid N2.
Next, remove the temperature probe from the sample rod. Unscrew the sample rod and fill the M?ssbauer chamber with He gas. Then, with the He gas flowing, withdraw the sample rod.
Close the sample chamber with a cap, and close the He valve.
Transfer the M?ssbauer sample into a secondary container filled with liquid N2. Then, carefully load the M?ssbauer sample cup into the rod-mounted sample holder, and tighten the set screw to secure the cup in the holder.
Brush away any ice on the sample holder and the rod. Then, immerse the sample holder in liquid N2, and open the He valve.
Insert the sample rod into the chamber and fix the rod in place with screws.
Then, stop the He flow and evacuate the sample chamber. Once the sample chamber is at the minimum pressure, stop the vacuum pump and allow a small amount of He?gas into the sample chamber. Finally, re-connect the temperature probe to the sample rod.
Open the gamma ray spectrometer interface to see a plot of the detector readings. Select the 14.4-keV peak and the 2-keV escape peak and hit the "Send to Windows" button.
Open the data collection software and set the source velocity range to 0 to 12 mm/s. Acquire data until the spectrum has achieved the desired resolution. Save the acquired data. Use appropriate software to fit the data and apply it to determine the isomer shift and the quadrupole splitting.
The M?ssbauer spectrum of ferrocene has a single quadrupole doublet with an isomer shift of 0.54 mm/s. When compared to typical ranges of isomer shifts for iron containing compounds, the isomer shift suggests either an Fe(II), S = 0 complex or an Fe(III), S = 5/2 complex.
From the proton NMR of ferrocene, it is known that the compound is a diamagnetic, neutral complex. Furthermore, its two cyclopentadienyl ligands each bear a charge of 1-, indicating that the iron center in ferrocene is in the 2+ oxidation state. Finally, based on the M?ssbauer result, it is evident that ferrocene has a spin state of 0.
M?ssbauer spectroscopy is widely used in inorganic chemistry. Let?s look at a few examples.
Iron-sulfur proteins contain Fe/S?clusters of two or more iron atoms bridged by S atoms. In a ferredoxin iron-sulfur protein, the diiron 2+ cluster contains two high-spin Fe(III) centers. Exchange coupling between these Fe centers results in an overall diamagnetic state with a spin of 0. The individual M?ssbauer spectra of each Fe center are indistinguishable from each other, so the spectrum of the ferredoxin shows only one quadrupole doublet.
Ferredoxins participate in electron transport by redox reactions at their Fe atoms. For example, a ferredoxin can accept an electron by a single-electron reduction at one of the Fe centers, resulting in a cluster with one high-spin Fe(III) center and one high-spin Fe(II) center. This appears as two superposed quadrupole doublets in the M?ssbauer spectrum.
Lipoyl synthase, which contains two 4-Fe/4-S?clusters, performs the final step of lipoyl cofactor synthesis. The proposed mechanism involves an intermediate with the substrate cross-linked to a degraded Fe/S cluster.
To investigate the properties of the reaction intermediate, M?ssbauer spectra were acquired in the presence and absence of a weak magnetic field. The resulting difference spectrum showed only the effects of an external magnetic field on the chemical shifts. The difference spectrum was combined with a simulated spectrum, revealing a 2:1 ratio from a mixed-valent Fe pair and an Fe(III) site.
You've just watched JoVE's introduction to M?ssbauer spectroscopy. You should now be familiar with the underlying principles of the M?ssbauer effect, the procedure for performing 57Fe M?ssbauer spectroscopy, and a few examples of how M?ssbauer spectroscopy is used in inorganic chemistry. Thanks for watching!
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Q1: What is the Mössbauer effect and why is it important for spectroscopy?
The Mössbauer effect occurs when a percentage of gamma ray emission and absorption events in crystal structures have negligible recoil, allowing resonance between identical nuclei in solids. This enables the gamma ray emitted by a relaxing nucleus to excite an identical nucleus, making precise nuclear spectroscopy possible without energy loss to recoil.
Q2: How does Doppler shift enable Mössbauer spectroscopy measurements?
The source and sample nuclei have slightly different energy gaps between ground and excited states due to different chemical environments. A Mössbauer spectrometer moves the gamma ray source back and forth at various speeds to induce a Doppler shift in the gamma rays, allowing resonant absorption to occur when the received gamma rays reach the precise energy needed to excite the sample.
Q3: What information does isomer shift reveal about an atom?
Isomer shift is the shift in resonance energy relative to the source and is directly related to the oxidation state of the atom. By comparing the measured isomer shift to known ranges for iron-containing compounds, chemists can determine whether an iron center is in a specific oxidation state, such as Fe(II) or Fe(III).
Q4: What causes quadrupole splitting in a Mössbauer spectrum?
Quadrupole splitting occurs when nuclear energy levels split due to a non-spherical surrounding electric field gradient, resulting in two distinct absorption energies. This interaction happens in asymmetric ligand environments and at nuclear spins greater than one-half, producing a quadrupole doublet with two peaks in the Mössbauer spectrum.
Q5: How does hyperfine splitting differ from quadrupole splitting in Mössbauer spectroscopy?
Hyperfine splitting occurs in an internal or external magnetic field, where each nuclear energy level splits into sub-states based on nuclear spin state. Unlike quadrupole splitting, which results from electric field gradients, hyperfine splitting produces multiple peaks—57Fe yields six allowed transitions, creating six peaks in the spectrum.
Q6: What does the Mössbauer spectrum of ferrocene reveal about its electronic structure?
Ferrocene's Mössbauer spectrum shows a single quadrupole doublet with an isomer shift of 0.54 mm/s, indicating an Fe(II), S = 0 complex. Combined with proton NMR data confirming the compound is diamagnetic and neutral, the spectrum reveals that ferrocene contains an iron center in the 2+ oxidation state with zero spin state. This analysis complements the structure determination ferrocene organometallic complex.
Q7: How is Mössbauer spectroscopy used to study iron-sulfur proteins?
Mössbauer spectroscopy characterizes iron-sulfur clusters in proteins like ferredoxins by detecting individual iron centers. Exchange coupling between Fe centers produces distinctive quadrupole doublets; when ferredoxins undergo single-electron reduction, the resulting mixed-valent cluster appears as two superposed quadrupole doublets, revealing changes in oxidation and spin states during electron transport.