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Mössbauer Spectroscopy: Advanced Inorganic Chemistry Seminar

Mössbauer spectroscopy is a technique used to characterize metal complexes. It works by measuring the absorption spectrum of modulated gamma quanta. Key parameters observed include isomer shift, which provides information about metal oxidation state and spin state, and quadrupole splitting, which gives insights into coordination environment and ligand charges. Magnetic dipole interactions can also be measured. The technique has disadvantages including requirements for a radioactive source and complex spectral interpretations.

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Jose Galvan
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114 views

Mössbauer Spectroscopy: Advanced Inorganic Chemistry Seminar

Mössbauer spectroscopy is a technique used to characterize metal complexes. It works by measuring the absorption spectrum of modulated gamma quanta. Key parameters observed include isomer shift, which provides information about metal oxidation state and spin state, and quadrupole splitting, which gives insights into coordination environment and ligand charges. Magnetic dipole interactions can also be measured. The technique has disadvantages including requirements for a radioactive source and complex spectral interpretations.

Uploaded by

Jose Galvan
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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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

9
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

13
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

14
15
Magnetic Dipol Interactions

16
Magnetic Dipol Interactions

17
Comparison of 57Fe (II) Mössbauer
spectra

[6]

large quadrupole splitting (3 mm/s)


despite Oh symmetry
18
Oh symmetry no quadrupole
splitting

C4v symmetry significant


quadrupole splitting
19
[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.

21

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