Mssbauer Spectroscopy

Fraser Parlane

Rudolf Mssbauer

Rudolf Ludwig Mssbauer, German physicist Nobel Prize in Physics, 1961 1929 - 2011 Explain it! The most important thing is, that you are able to explain it! You will have exams, there you have to explain it. Eventually, you pass them, you get your diploma and you think, that's it! No, the whole life is an exam, you'll have to write applications, you'll have to discuss with peers... So learn to explain it! You can train this by explaining to another student, a colleague. If they are not available, explain it to your mother or to your cat! Rudolf Ludwig Mssbauer, 1984

The M ssbauer Effect Common spectroscopy techniques

Has similarities to NMR spectroscopy

The M ssbauer Effect observing resonance-fluorescence and the Compton Effect

The Compton effect can be a nuisance. Jeremy Bernstein

Initially

= 2 =

Change in wavelength = (1 cos ) Sponge / steel wall analogy

Energies emitted

Energies absorbed

Graph not to scale

The M ssbauer Effect observing resonance-fluorescence

Two main issues with this technique: 1. The recoil of the nucleus as the gamma-ray is emitted or absorbed 2. The splitting caused in the energy levels by the electronic and magnetic environment cause hyperfine splitting in the energy levels

The M ssbauer Effect The Discovery

Mossbauer discovered that when the atoms are within a solid matrix the effective mass of the nuclei is much larger. Mass is now effectively the mass of the system This makes and very small RESONANCE! Resolution is now vastly increased (1 in 1012 )

Paper / sun comparison

The M ssbauer Effect The Discovery

High resolution allows for detection of hyperfine splitting. Requirements for high resolution: Requires low lying excited states (lower) Lifetime of the excited state (longer) meets both of these requirements and is commonly used Resonnance!
57Fe

The M ssbauer Effect The Discovery

Introduction M ssbauer Spectroscopy Fundamentals

Hyperfine interactions (billionth of an electron volt) this requires very small changes in the energy of the gamma-ray radiation. This is done using the Doppler effect.

Introduction M ssbauer Spectroscopy Reading the Spectra

Three properties that can be read from the spectra

1. Isomer shift
2. Quadrupole Splitting 3. Magnetic Splitting

Introduction M ssbauer Spectroscopy Isomer Shift

Shift cannot be measured directly. It needs to be measured relative to a known absorber. For instance, 57Fe is often calibrated to alpha iron. Analogous to NMR. Measured as centroid of the spectrum. Used to determine valency states, ligand bonding states, electron shielding and the electronegativity of functional groups (the electric environment). Less electron shielding leads to positive isomer shift Example Fe2+ Fe3+ 3d 3d
6 5

More electron shielding Less electron shielding

positive shift negative shift

Introduction M ssbauer Spectroscopy Quadrupole Splitting

Nuclei with a quantum number > 2 have an asymmetrical charge, forming a nuclear quadrupole moment. = 2 The principle component of the EFG Quadrupole moment A constant

Introduction M ssbauer Spectroscopy Magnetic Splitting

Zeeman splitting is the result of the nucleus interacting with a magnetic field = + + + From the spin on the electrons polarizing the spin of the nucleus From the orbital moment of those electrons From the dipolar field due to the spin on those electrons

Splits the field into 2 + 1 peaks.

Introduction M ssbauer Spectroscopy Magnetic Splitting

For 57Fe, this gives six possible transitions for 3 1 magnetic quantum numbers 2 and 2 transition.

Peak intensities

4 sin2 3 1 1 + cos2

Introduction M ssbauer Spectroscopy The Machine

Introduction M ssbauer Spectroscopy Applications

Sensitive to subtle changes in the environment Detection limits in the billionth of an electron volt Geology Moon Structure and function of enzymes Analysis of heterobimetallic complexes

References

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15.

16.
17. 18. 19.

20.

International Board on the Applications of the Mssbauer Effect (IBAME) and Mssbauer Effect Data Center (MEDC),Mssbauer Effect website Accessed June 3, 2010 Gtlich, J.M.; The Principle of the Mssbauer Effect and Basic Concepts of Mssbauer Spectrometry Mssbauer Spectroscopy Group, Royal Society of Chemistry (RSC) website, Introduction to Mssbauer Spectroscopy Part 1 Accessed June 3, 2010 Longworth, G; Window, B (1971). "The preparation of narrow-line Mssbauer sources of 57Co in metallic matrices". Journal of Physics D 4 (6): 835.Bibcode:1971JPhD....4..835L. doi:10.1088/0022-3727/4/6/316. Mssbauer Spectroscopy Group, Royal Society of Chemistry (RSC) website, Introduction to Mssbauer Spectroscopy Part 2 Accessed June 3, 2010 P. Gtlich, J.M. Greneche, F.J. Berry; Mssbauer Spectroscopy: A Powerful Tool in Scientific ResearchAccessed June 3, 2010 Walker, L.; Wertheim, G.; Jaccarino, V. (1961). "Interpretation of the Fe57 Isomer Shift". Physical Review Letters 6 (3): 98. Bibcode:1961PhRvL...6...98W.doi:10.1103/PhysRevLett.6.98. Mssbauer Effect Data Center Klingelhfer, G. (2004). "Mssbauer in situ studies of the surface of Mars". Hyperfine Interactions 158 (14): 117 124. Bibcode:2004HyInt.158..117K. doi:10.1007/s10751-005-9019-1. Sarkar, A. et al. (2007). "FischerTropsch Synthesis: Characterization Rb Promoted Iron Catalyst". Catalysis Letters 121 (12): 111. doi:10.1007/s10562007-9288-1. Burger, K.; Nemes-Vetssy, Zs.; Vrtes, A.; Afanasov, M. I. (1986). "Mssbauer spectroscopic study of the oxidation state of antimony in antimony sulfides of different composition". Journal of Crystallographic and Spectroscopic Research 16 (2): 295.doi:10.1007/BF01161115. Chen, Y.-L.; Yang, D.-P. (2007). "Recoilless Fraction and Second-Order Doppler Effect". Mssbauer Effect in Lattice Dynamics. John Wiley & Sons.doi:10.1002/9783527611423.ch5. ISBN 978-3-527-61142-3. Lynch, J.B.; Juarez-Garcia, C; Mnck, E; Que Jr, L (1989)."Mssbauer and EPR studies of the binuclear iron center in ribonucleotide reductase from Escherichia coli. A new iron-to-protein stoichiometry". Journal of Biological Chemistry264 (14): 80916. PMID 2542262. Elgren, T.E.; Lynch, JB; Juarez-Garcia, C; Mnck, E; Sjberg, BM; Que Jr, L (1990). "Electron Transfer Associated with Oxygen Activation in the B2 Protein of Ribonucleotide Reductase from E. Coli". Journal of Biological Chemistry 266 (29): 192658. PMID 1918044. B.G. Fox; Surerus, KK; Mnck, E; Lipscomb, JD (1988)."Evidence for a mu-oxo bridged binuclear iron center in the hydroxylase component of methane monooxygenase. Mssbauer and EPR studies". Journal of Biological Chemistry 263 (22): 105536. PMID 2839495. Fox, B.G. et al. (1993). "Mssbauer, EPR, and ENDOR Studies of the Hydroxylase and Reductase Components of Methane Monooxygenase from Methylosinus Trichosporium OB3B". Journal of the American Chemical Society 115 (9): 36883701. doi:10.1021/ja00062a039. Gupta, R.; Fu, R.; Liu, A.; Hendrich, M. P. (2010). "EPR and Mssbauer spectroscopy show inequivalent hemes in tryptophan dioxygenase". Journal of the American Chemical Society 132 (3): 1098109.doi:10.1021/ja908851e. PMID 20047315. Vu, V. V. et al. (2009). "Human deoxyhypusine hydroxylase, an enzyme involved in cell growth,activates O2 with a nonheme diiron center". Proceedings of the National Academy of Sciences 106 (35): 148149.Bibcode:2009PNAS..10614814V.doi:10.1073/pnas.0904553106. PMC 2736468.PMID 19706422. Volgel, S.A.; Dege, JE; Perkins-Olson, PE; Jaurez-Garcia, CH; Crawford, RL; Mnck, E; Lipscomb, JD (1993)."Purification and Characterization of Protocatechuate 2,3 Dioxygenase from Bacillus macerans: a New Extradiol Catecholic Dioxygenase". Journal of Bacteriology 175(14): 4414 26. PMC 204882. PMID 8392511. B.H. Zimmermann (1988). "Properties of a Copper-Containing Cytochrome ba3: A Second Terminal Oxidase from the Extreme Thermophile Thermus thermophilus".Proceedings of the National Academy of Sciences 85 (16): 57797783. Bibcode:1988PNAS...85.5779Z.doi:10.1073/pnas.85.16.5779.