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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    The European physical journal 10 (1999), S. 271-275 
    ISSN: 1434-6036
    Keywords: PACS. 64.30.+t Equations of state of specific substances - 64.60.Cn Order-disorder transformations; statistical mechanics of model systems
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract: It is well-known that 1D systems with only nearest neighbour interaction exhibit no phase transition. It is shown that the presence of a small long range interaction treated by the mean field approximation in addition to strong nearest neighbour interaction gives rise to hysteresis curves of large width. This situation is believed to exist in spin crossover systems where by the deformation of the spin changing molecules, an elastic coupling leads to a long range interaction, and strong bonding between the molecules in a chain compound leads to large values for nearest neighbour interaction constants. For this interaction scheme an analytical solution has been derived and the interplay between these two types of interaction is discussed on the basis of experimental data of the chain compound which exhibits a very large hysteresis of 50 K above RT at 370 K. The width and shape of the hysteresis loop depend on the balance between long and short range interaction. For short range interaction energies much larger than the transition temperature the hysteresis width is determined by the long range interaction alone.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of materials science 32 (1997), S. 6579-6581 
    ISSN: 1573-4803
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A light-induced excited spin state trapping (LIESST) experiment for a thermal gradual spin crossover complex, Fetris (2-pyridylmethyl) amine(NCS)2 or Fe(tpa) (NCS)2, was attempted for the first time. The high spin (HS) state after light inducement stayed metastable over a period of days without relaxation at 10 K. Intersystem relaxation from a high to a low spin (LS) complex occurred at 50 K after bleaching at 10 K. Investigation of the Mossbauer spectra of the LIESST and relaxation experiment indicated that the Debye–Waller factor was a correlation parameter of the HS fraction and that the co-operative effect played a role in the relaxation process for such a solid compound.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1572-9540
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: 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%.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Hyperfine interactions 113 (1998), S. 331-339 
    ISSN: 1572-9540
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: 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.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1572-9540
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: 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.
    Type of Medium: Electronic Resource
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