Mössbauer spectroscopy:

History, principles and potential

analysis of materials
@ Nuclear gamma resonance spectroscopy
15/10/2019
Materials Characterisation and Analysis

Elemental/Chemicals analyses – XRF, ICP, EDS, Ion/Gas Chromatography,

NAA
Physical Properties (Including Mechanical Properties) – Particle Analyser,
Density (Bulk & Powder), Vickers Micro/Nano-hardness, Universal Tester
Thermal Analyses – TGA, DTA, DSC, Thermal Diffusivity (i.e. Laser Flash
Method)
Structural Properties – FTIR, XRD, XPS, NMR, Mӧssbauer Spectroscopy,
EPR, Raman Spectroscopy, XANES Spectroscopy
Microscopy (Microstucture, Surface Morphology) – SEM, TEM, OM, AFM,
Optical Profilometer
Electrical Properties – IS, NA, 4/2-point Probes
 Introduction
Idea from Rudolf L. Mössbauer
o Born in Munich, German
o Discovered Mössbauer Effect
o Won Nobel Prize in 1961 in physics
o Passed away in 2011

1958 - Major breakthrough in nuclear gamma resonance

phenomena
o Working with 129-keV gamma ray of 191Ir
o Discovered by imbedding the radioactive samples in crystals, and
cooling them, their tightly held crystal positions prevented them from
recoiling. The energy of recoil had been absorbed by the lattice as a
whole.

R.L. Mössbauer made his first observation of recoilless nuclear

resonant absorption in 191Ir!
 Mössbauer Effect - recoil emission and
resonant absorption of gamma radiation
Free emitting and absorbing gamma ray

Emission Absorption

Not useful for Mossbauer

spectroscopy

When gamma ray is emitted a nuclei will recoil in conservation of momentum

 Mössbauer Effect – recoil-free emission and
resonant absorption of gamma radiation
Emitting and absorbing atoms fixed in a lattice
2
E 
Emission Absorption ER = 2
2mc

Enabling Mossbauer
spectroscopy

Atoms placed in solid matrix have much greater effective mass. Recoil mass of
nuclei becomes recoil mass of entire matrix
Instrumentation
Schematic of Mossbauer Spectroscopy
Gamma ray sources

Most frequently used isotopes: 57Fe, 119Sn, 121Sb, 129I

Mossbauer source
57Co
I=7/2

I=3/2 136 keV

9% 91 %
57Fe

I=5/2 14.4 keV

Mössbauer
γ ray
I=1/2 0 keV

half live of ~271 days

 Interaction of sample with source
Circumstances of resonance - What does this means?
◦ With the use of the Doppler effect the wavelength of the source gamma rays can be tuned
◦ When this wavelength is the same as the wavelength of emitted gamma ray resonance is achieved
 Nuclear Hyperfine Interactions Observable with Mossbauer Spectroscopy
Observed Effect Illustration Observed Spectrum
Isomer Shift
Interaction of the nuclear charge
distribution with the electron cloud
surrounding the nuclei in both the
absorber and source

Zeeman Effect(Dipole Interaction)

Interaction of the nuclear magnetic
dipole moment with the external
applied magnetic field on the
nucleus.

Quadrupole Splitting
Interaction of the nuclear electric
quadrupole moment with the EFG
and the nucleus
Detectors
Data analysis

Recoil software package (version 1.03)

Usage and Application
 Mossbauer Spectroscopy in Biology

• Used in combination with other

data to obtain chemical
information about proteins
 Mossbauer Spectroscopy in Space

• Used on Mars

• Rovers have miniature

mossbauer spectrometers

http://www.medc.dicp.ac.cn/Mesite/images/Klingelhofer2.gif
 Mossbauer Spectroscopy in Physics and
Chemistry
Used to further pursue the nature of energy states in nuclei

Measure changes in chemical environment of nuclei

Monitor materials during phase changes

Monitor chemical reactions

Determine structures of molecules

 Mossbauer Spectroscopy in Biology

• Used in combination with other

data to obtain chemical
information about proteins
 Mossbauer Spectroscopy in Physics and
Chemistry
Used to further pursue the nature of energy states in nuclei

Measure changes in chemical environment of nuclei

Monitor materials during phase changes

Monitor chemical reactions

Determine structures of molecules

 Drawbacks of Mossbauer Spectroscopy
Must be in solid crystalline structure

Minute hyperfine interactions

◦ Overcome with the use of Doppler Effect

Major limitation is that it is a “bulk” technique

◦ Often times large amounts of sample are needed for analysis
◦ Recent improvements in electronics and detectors are helping to overcome

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 Strengths and weaknesses of 57Fe Mössbauer
spectroscopy
Strengths Weaknesses
Sensitive only to 57Fe Sensitive only to 57Fe
(no matrix effects) (“sees” only 57Fe)
Sensitive to oxidation state Coordination ? to ±
Allows distinction of magnetic Paramagnetic phase data often
phases ambiguous
Very sensitive towards magnetic Diamagnetic element substitution
phases & relaxation
Non-destructive Slow
Resolution limited by uncertainty If possible, use other techniques
principle as well
Often a combination of Mössbauer spectroscopy with other techniques can help solve
problems that cannot be resolved using Mössbauer spectroscopy alone.
Conclusions
Wide application across multiple scientific disciplines
Relatively cheap method
Relatively fast method
Give valuable information on chemical environment within molecule
◦ Isomer Shifts
◦ Quadrupole splitting
◦ Magnetic splitting

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