Mössbauer Spectroscopy

Advanced Inorganic Chemistry

Seminar

Presentation in WS 2011/2012
Annkatrin Lennert, Carina Bronnbauer, Eva Kränzlein,
Kerstin Krebs, Kristin Brunner, Sven Herrmann, Dominik Halter
 Motivation & Utilization
Where is Mössbauer Spectrospy applied?

Characterization of Metal Complexes

What is Mössbauer Spectroscopy good for?

Determination of • Oxidation states
• Spin States (correlated to bond length)
• Magnetic Behaviour
• Ligand Information

Spectroscopy Principle?
Absorption Spectrum of modulated gamma quanta
2
 Theory of Mössbauer spectroscopy

Mössbauer effect: recoil-free emission and resonant absorption of radiation

Example: 57Fe nuclear resonance
E
Excited state -ER +ER
(live time: = 97 ns)

E =14,4keV E
= 86 pm

Ground state
E Energy
E = E – ER + ? E = E + ER + ?
Source Sample
: line width
h h: Planck constant

Heisenberg uncertainty principle: = = 6,75e-9 eV
2 : live time
Small changes in frequency inhibt the resonance
effect between source and absorber
p = mv p = (h )/c
mv2 p2 (h )2

Recoil energy: ER= = = ER = 1,95e-3 eV
2 2m 2mc2 3
 Theory of Mössbauer spectroscopy

Useing the Doppler Effect to affect the frequency:
Moveing the source leads to a change in the frequency of the emitted quantum

0
: frequency of the emitted photon
v : velocity of the source
= 0+ 0 a a
: new frequency
c
c: light velocity

to be in the dimension of 1mm s-1 to achieve resonace effects between the source
0 has
and the absorber
E = E - ER + ED

Construction of the measuring equipment

E
26
Co57
Source Fe57
quantum e- capture 26 136 keV
1
(85%)
14,4 keV
-va +va Absorber Detector
2
(11%)
E
4
 Theory of Mössbauer spectroscopy

Creation of a Mössbauer spectrum

va = 0
Maximum overlap
ES , EA Energy

va > 0
Partial overlap
ES EA Energy

va < 0
Partial overlap
ES EA Energy
Rel. Transmission [%]

Resonance
absorption line

Velocity mm/s
5
 Sample preparation

• Low resonance absorption conditional for Mössbauer spectroscopy

• → solid sample can distribute recoil energy in the crystal lattice

• Energy levels in atom are quantized

→ limited probability f of absorbing a γ-quant
without accompanying phonon transition = recoilless absorption
is given by the Lamb-Mössbauerfactor

• → recoilless emission and absorption favoured at deep temperatures

6
 Common samples for Mössbauer
spectroscopy

Important factors:
- Suitable half-life time of the parent isotop
- Low gamma-ray energy to gain sufficent signal-to-noise ratio

Most frequently used isotops are: 57Fe, 119Sn, 121Sb and 129I
7
Isomer Shift δ

8
 Isomer Shift δ
Reasons for isomer shift:
- electron density at the nucleus is different for ground and excited state
- unlike coloumb interactions

Measurement of electron density at the nucleus

Information about:
• Oxidation state of the Mössbauer atom.
• Bonding properties in case of coordination compounds (covalency)
• Delocalization of d-electrons due to back-bonding or shielding-effects of s-electrons
• Electronegativity of ligands

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 Isomer Shift δ
keep in mind: Due to many possibilities affecting isomer shift there can´t be any
absolute value for δ – but you can tell about trends!

Example: 57Fe-Mössbauer with (δR/R) beeing negative

"The higher the oxidation state the lower is the isomer-shift!"

10
n

11
 y

e.g.

12
Quadrupol Splitting

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 Information

Molecule symmetry, oxidationstate,

coordination, steroechemistry

Trans ∆EQ = 3.0 – 4.0 mm/s
X
R
R Sn
R
X

Cis ∆EQ = 1.7 – 2.4 mm/s

X
R
X Sn
R
R

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15
Magnetic Dipol Interactions

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Magnetic Dipol Interactions

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 Comparison of 57Fe (II) Mössbauer
spectra

[6]

large quadrupole splitting (3 mm/s)

despite Oh symmetry
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 Oh symmetry no quadrupole
splitting

C4v symmetry significant

quadrupole splitting
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[6]
 Summary
Technique: Absorption Spectrum of modulated gamma quanta
(Doppler effect)

Observed parameters:
Isomer Shift Quadrupol Splitting

s-Electr. (nucleus) Quadrupol momentum of nucleus

Interacting with Field [ I > ½ ] !

• Metal oxidation State

• Spin state ( bondlength) • Metal valence e- [non cubic]
• Coordination environment • Ligand charges

• Radio active source / synchrotron radiation

Disadvantages:
• Interpretation difficulties due to interaction overlay 20
 References

[1] http://www.uni-muenster.de/imperia/md/content/physikalische_chemie/app_moess.pdf

[2] http://uni-leipzig.de/~energy/pdf/freusd9.pdf

[3] http://ruby.chemie.uni-freiburg.de/Vorlesung/methoden_I_5.xhtml

[4] Organometallchemie, Christoph Elschenbroich, Vieweg & Teubner Verlag (2008)

[5] Anorganische Chemie, Erwin Riedel, Gruyter; Auflage: 6. A. (2007)

[6] P. Gütlich, Z. anorg. allg. Chem 2012, 638 (1), 15.

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