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  • 1
    Digitale Medien
    Digitale Medien
    Springer
    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 231-235 
    ISSN: 0392-6737
    Schlagwort(e): Mössbauer spectra ; Structure, bonding, conformation, configuration and isomerism of biomolecules ; Conference proceedings
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Physik
    Notizen: Summary Using the possibility to produce61Co sources at the MAinz MIcrotron,61Ni Mössbauer spectroscopy was applied to different kinds of chemical problems. Measurements of isomer shifts andV zz values in some common compounds and compounds with unusual chemical bonding for comparison with band structure calculations, measurement of61Ni Mössbauer parameters in model compounds for hydrogenase and dehydrogenase with an active [NiS4] centre, and study of novel binary NiF3 compounds at helium temperature are presented.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Applied physics 62 (1996), S. 317-322 
    ISSN: 1432-0630
    Schlagwort(e): PACS: 68.65; 76.00
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau , Physik
    Notizen: Abstract.  Oxidic and metallic iron and iron/nickel multilayers, formed after thermal and chemical treatment of Langmuir-Blodgett films, were investigated. Reduced iron-stearate multilayers were compared with evaporated films concerning their phase composition and their lateral homogeneity. The sequence of metallic and oxidic iron in the films after reduction was determined. Oxidic iron/nickel mixed layers can be prepared from Langmuir-Blodgett films, in which a magnetically non-ordered Fe3+ phase exhibiting a distribution of the quadrupole splitting is observed. After reduction of such layers, two metallic iron phases appear dependent on the nickel concentration. The hyperfine field distribution of the magnetically ordered metallic phase can be evaluated using a method proposed by Rancourt.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    Springer
    Applied physics 62 (1996), S. 317-322 
    ISSN: 1432-0630
    Schlagwort(e): 68.65 ; 76.00
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau , Physik
    Notizen: Abstract Oxidic and metallic iron and iron/nickel multilayers, formed after thermal and chemical treatment of Langmuir-Blodgett films, were investigated. Reduced iron-stearate multilayers were compared with evaporated films concerning their phase composition and their lateral homogeneity. The sequence of metallic and oxidic iron in the films after reduction was determined. Oxidic iron/nickel mixed layers can be prepared from Langmuir-Blodgett films, in which a magnetically non-ordered Fe3+ phase exhibiting a distribution of the quadrupole splitting is observed. After reduction of such layers, two metallic iron phases appear dependent on the nickel concentration. The hyperfine field distribution of the magnetically ordered metallic phase can be evaluated using a method proposed by Rancourt.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Springer
    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 107-136 
    ISSN: 0392-6737
    Schlagwort(e): Crystal and ligand fields ; Mossbauer effect ; other γ-ray spectroscopy ; Visible and ultraviolet spectra ; Conference proceedings
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Physik
    Notizen: Summary Coordination compounds of transition metal ions with open-shell electron configurations may exhibit dynamic electronic-structure phenomena, depending on the nature of the coordinating ligand sphere. The change of spin state with temperature («thermal spin-crossover»), light-induced electron transfer processes leading to long-lived metastable charge and spin states (e.g., «LIESST» effect), are some of the fascinating electronic games encountered in transition metal compounds, which are presently under extensive study by chemists and physicists. Mössbauer spectroscopy plays a dominant role in the investigation of such phenomena in iron compounds, as will be demonstrated in this paper. This work will focus on selected examples of «thermal spin-crossover» in iron(II) complexes and switching between different spin states by irradiation with light of different wavelength (LIESST effect), demonstrating that Mössbauer spectroscopy besides other physical techniques proves to be a highly elegant tool for following the spin state conversion and the concomitant changes of molecular and crystal structure properties. Finally, Mössbauer emission spectroscopy, both time integral and time differential, has been employed to generate and identify long-lived excited spin states by making use of the nuclear disintegration of57Co as an intrinsic molecular light source (NIESST=nuclear decay-induced excited-spin-state trapping). Lifetime measurements by optical techniques on LIESST states and by time-differential Mössbauer coincidence spectroscopy on NIESST states prove that the relaxation pathways in the mechanisms for LIESST and NIESST are identical.
    Materialart: Digitale Medien
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  • 5
    ISSN: 1434-6079
    Schlagwort(e): PACS. 33.15.Vb Correlation times in molecular dynamics - 33.15.Hp Barrier heights (internal rotation, inversion, rotational isomerism, conformational dynamics) - 33.25.+k Nuclear resonance and relaxation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Physik
    Notizen: Abstract: 19 F and 11 B spin-lattice relaxation times were measured in [ Zn ( ptz ) 6 ] ( BF 4 ) 2 and in the spin-crossover compound [ Fe ( ptz ) 6 ] ( BF 4 ) 2 . For both compounds BF 4 - anion reorientation is active above 50 K. For [ Zn ( ptz ) 6 ] ( BF 4 ) 2 , the anion-reorientation dynamics is different in the temperature regions of 50-90 K, 90-120 K, and above 150 K; between 120 and 150 K it changes rapidly reflecting a structural change. In [ Fe ( ptz ) 6 ] ( BF 4 ) 2 the mechanism for the paramagnetic relaxation involving the 19 F nuclei is found to be of the diffusion-limited type according to the theory of Lowe and Tse. The present results prove that the spin-crossover takes place in a dynamic surrounding and not in a static crystal lattice.
    Materialart: Digitale Medien
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  • 6
    ISSN: 1572-9540
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Physik
    Notizen: Abstract The Lamb-Mössbauer Factor (LMF) of molecular crystals is expected to depend on the electronic molecular states by their different intramolecular vibrational frequencies. Revisiting Mössbauer spectra obtained by time differential Mössbauer emission spectroscopy of the low spin compound [57Co/Mn(bipy)3](PF6)2 (bipy= 2,2'-bipyridine) a ratio of 1.25 for the LMFs of the low spin ground state and of an excited high spin state decaying in the Mössbauer time window could be evaluated. The difference found is in line with the change of LMF observed for spin crossover compounds where the excited high spin state is populated by the so‐called LIESST effect. The initial population of the high spin state is close to 100%.
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    Springer
    Hyperfine interactions 113 (1998), S. 331-339 
    ISSN: 1572-9540
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Physik
    Notizen: Abstract Tris(2,2'-bipyridyl)-57CoII and bis(2,2':6',2'-terpyridine)-57CoII complexes were synthesised in the supercages of zeolite‐Y in order to study the effect of molecular isolation on the aftereffects of the 57Co(EC)57Fe decay. As compared to the regular crystalline salts of the complex ions where, according to the emission Mössbauer spectra, the most abundant species is low‐spin FeII, the molecular isolation in the zeolite resulted in a larger fraction of low‐spin FeIII and a varying amount of high‐spin Fe2+ species. In the investigated temperature range, 20 K to 295 K, the majority of the changes was observed above 80 K. In the case of tris (2,2'-bipyridyl)-57CoII-Y, the most characteristic change occurred in valence states, while for bis (2,2':6',2'-terpyridine)-57CoII‐Y, the temperature dependence of the spin states was more prominent. The change in the low spin valence states is explained partly by donor-acceptor properties of the zeolite lattice. The variation in the high spin fraction is explained by radiation damage of the ligand sphere and/or fragmentation of the complex ion followed by incomplete recombination in the supercage. Molecular isolation itself did not seem to increase the chance of fragmentation (as a consequence of charge neutralization following Auger ionization) of these highly conjugated complex molecules.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Springer
    Hyperfine interactions 95 (1995), S. 107-128 
    ISSN: 1572-9540
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Physik
    Notizen: Abstract In a first approximation the Debye-Waller factor (DWF) of molecular crystals is factorized into a molecular and a lattice part:f=f m f l. In the case of spincrossover compounds there is the unique possibility to measure differences of both parts in the two spin states by switching the spin states with the LIESST effect. Measurements of the DWF depending on temperature, γ-ray direction and spin state were performed with57Fe-Mössbauer spectroscopy on three single crystals (R¯3) of the spincrossover system [FexZn1−x(ptz)6](BF4)2 (ptz=1-propyltetrazole), a concentrated sample withx=1 and diluted ones withx=0.30 andx=0.005. The DWF decreases from 10 to 300 K by a factor of ∼ 100 and its anisotropyf ⊥/f ∥ increases from ∼ 1 to 5.4. The differences of the DWF in the low spin and the high spin state (after LIESST) for the diluted and the concentrated samples were measured at low temperatures (≤ 50 K). From these data both the Grüneisen constant of the lattice γG=2.9 and the lowest IR active intramolecular frequency (45 cm−1 (HS), 58 cm−1 (LS)) have been determined. The contribution of the DWF from the acoustic modes of the lattice is calculated from the elastic constants of rhombohedral [Fe x Zn1−x (ptz)6](BF4)2. The contribution of the optical lattice vibrations is estimated. The influence of different DWF in the two spin states on the evaluation of the fraction of molecules in either spin state from Mössbauer area data is discussed.
    Materialart: Digitale Medien
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  • 9
    ISSN: 0947-6539
    Schlagwort(e): iron complexes ; magnetic susceptibility ; Mössbauer spectroscopy ; phasetransitions ; spin crossover ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The iron(II) complex [Fe(bpp)2]-(CF3SO3)2 H2O (bpp = 2,6-bis(pyrazolyl-3-yl)pyridine) shows a thermal spin transition associated with a hysteresis of approximately 140 K width. The transition temperatures T1/2 (where the fraction of HS species γHS = 0.5) are 147 K and ≍285 K in the cooling and heating directions, respectively. The compound shows the LIESST and reverse-LIESST effects at low temperatures. The relaxation of the metastable HS states generated by LIESST was observed quantitatively at temperatures between 77.5 and 85 K by Mössbauer spectroscopy. Metastable HS states can also be generated by rapid cooling of the sample. The relaxation of the metastable HS states formed by thermal spin-state trapping was monitored at temperatures between 104 and 118 K by magnetic susceptibility measurements. The relaxation mechanisms of the HS states generated by LIESST and thermal spinstate trapping are completely different. We suggest that the HS → LS relaxation after thermal spin-state trapping is triggered by an additional structural phase transition of the system.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    Springer
    Fresenius' Zeitschrift für analytische Chemie 353 (1995), S. 723-728 
    ISSN: 1618-2650
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract By thermal and chemical treatment of Langmuir-Blodgett (LB) films, oxidic and metallic Fe and Ni layers can be prepared. The films are characterised, where differences e.g. in the lateral homogeneity are found. The metallic Fe containing samples show a higher corrosion stability as compared with films prepared by other coating techniques. Mixed Fe/Ni oxidic and metallic layers, respectively, are prepared, where the Ni concentration in the oxidic films can be determined as a function of the ratio of initially transferred numbers of LB layers. The phase composition of the metallic Fe changes systematically with the Ni concentration.
    Materialart: Digitale Medien
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