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Asymmetry in Mössbauer spectra of FeIII-azaporphyrin complexes

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Konferencja
Proceedings of the All-Polish Seminar on Mössbauer Spectroscopy OSSM'06, June 18-21, 2006, Koszęcin, Poland
Języki publikacji
EN
Abstrakty
EN
Temperature dependence of asymmetry as well as isomer shift and quadrupole splitting values of Mössbauer spectra of trivalent iron complexes coordinated to porphyrin ligands such as octaethylporphyrin, monoazaethioporphyrin, diazaoctaethylporphyrin and phthalacyanine is discussed in this paper. All the above mentioned complexes have the chloride axial ligand at the fifth coordination site. Different temperature changes of asymmetry and other parameters of Mössbauer spectra of these complexes can be correlated with a number of methine bridges CH substituted by nitrogen atoms in the porphyrin macrocycle. The form of this asymmetry is such that the higher-energy component of the doublet is more broadened than the lower-energy one, while the areas (intensities) under each of two components are the same. The most distinct asymmetry is observed at room temperature. When temperature is decreasing, the spectrum becomes successively more symmetrical and at liquid helium temperature linewidths of both components of the quadrupole splitting are very close one another. The Mössbauer spectrum of the FeCl-monoazaethioporphyrin complex exhibits reversed asymmetry at liquid helium temperature in comparison with the spectra of the remaining complexes i.e. the lower-energy component of the doublet is slightly more broadened than the higher-energy one. The spin-spin and spinlattice relaxation mechanisms in the context of quantum mechanically mixed spin states S = 5/2 + 3/2 of FeIII ions are considered as a source of the observed asymmetry.
Czasopismo
Rocznik
Strony
93--98
Opis fizyczny
Bibliogr. 22 poz., rys.
Twórcy
autor
autor
  • Institute of Physics, Częstochowa University of Technology, 19 Armii Krajowej Str., 42-200 Częstochowa, Poland, Tel./Fax: +48 34 3250795, dzil@mim.pcz.czest.pl
Bibliografia
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  • 7. Dzilinski K (2000) Unusual linewidth in Mössbauer spectra of methoxy-FeIII-octaethylporphyrin complex. Mol Phys Rep 30:38−43
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  • 13. Kadish KM, Smith KM, Guilard G (eds) (2000) The porphyrin handbook. Vol. 6. Academic Press, San Diego
  • 14. Kobayashi N (2000) Meso-azaporphyrins and their analogues. In: Kadish KM, Smith KM, Guilard R (eds) The porphyrin handbook. Academic Press, San Diego. Vol. 3, pp 301−321
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  • 19. Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation. Phys Rev Lett 77:3865−3868
  • 20. Sams JR, Tsin TB (1979) Mössbauer spectroscopy of iron porphyrins. In: Dolphin D (ed) The porphyrins. Academic Press, New York-San Francisco-London. Vol. 4, pp 425−475
  • 21. Shenoy GK, Wagner FE, Kalvius GM (1978) The measurement of the isomer shift. In: Shenoy GK, Wagner FE (eds) Mössbauer isomer shifts. North-Holland Publishing Company, Amsterdam-New York-Oxford,pp 49−110
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Typ dokumentu
Bibliografia
Identyfikator YADDA
bwmeta1.element.baztech-article-BUJ6-0011-0056
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