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The theory of heterodyne/stroboscopic detection of nuclear resonance scattering is developed, starting from the total scattering matrix as a product of the matrix of the reference sample and the sample under study. This general approach holds for any dynamical scattering channel. The forward channel, which is discussed in detail in the literature, reveals the speciality that electronic scattering causes only an energy independent diminution of the intensity. For all other channels, complex resonance line shapes in the heterodyne/stroboscopic spectra - as a result of interference of electronic and nuclear scattering - is encountered. The grazing incidence case is evaluated and described in detail. Experimetal data of classical grazing incidence reflection and their stroboscopic detection on [natFe/57Fe]10 and antiferromagnetic [57Fe/Cr]20 multilayers are fitted simultaneously., 23 pages, 4 Postscript figures, uses iucr.sty

Scientific reports 7, 43114 (2017). doi:10.1038/srep43114, Reciprocity is when wave or quantum scattering satisfies a symmetry property, connecting a scattering process with the reversed one. While reciprocity involves the interchange of source and detector, it is fundamentally different from rotational invariance, and is a generalization of time reversal invariance, occurring in absorptive media as well. Due to its presence at diverse areas of physics, it admits a wide variety of applications. For polarization dependent scatterings, reciprocity is often violated, but violation in the phase of the scattering amplitude is much harder to experimentally observe than violation in magnitude. Enabled by the advantageous properties of nuclear resonance scattering of synchrotron radiation, we have measured maximal, i.e., 180-degree, reciprocity violation in the phase. For accessing phase information, we introduced a new version of stroboscopic detection. The scattering setting was devised based on a generalized reciprocity theorem that opens the way to construct new types of reciprocity related devices., Published by Macmillan, London

The effect of selfabsorption in Mossbauer sources is studied in detail. Spectra were measured using an old 57Co/Rh source of 74MBq activity with an original activity of ca. 3.7GBq and a 0.15GBq57Co/α − Fe source magnetized by an in-plane magnetic field of 0.2 T. The 57Co/α − Fe source of a thickness of 25 μ was used both from the active and the inactive side giving cause to very different selfabsorption effects. The absorber was a single crystal of ferrous ammonium sulphate hexahydrate (FAS). Its absorption properties were taken over from a detailed study (Bull et al., Hyperfine Interact. 94(1–3), 1; Spiering et al. 2). FAS (space group P21/c) crystallizes as flat plates containing the (\(\overline {2}\)01) plane. The γ-direction was orthogonal to the crystal plate. The 57Co atoms of the 57Co/Rh source were assumed to be homogeneously distributed over a 6μ thick Rh foil and to follow a one dimensional diffusion profile in the 25 μ Fe-foil. The diffusion length was fitted to 10 μ. The theory follows the Blume-Kistner equations for forward scattering (Blume and Kistner, Phys. Rev. 171, 417, 3) by integrating over the source sampled up to 128 layers.

The superstructure recently discovered in [Fe(pic)3]Cl2.EtOH at temperatures inside the step region of the high-spin–low-spin transition curve sheds new light on the anomalous transition behaviour in spin crossover compounds. The structure of the metastable LIESST state of [Fe(pic)3]Cl2.EtOH at 10 K has been measured. The decay has been followed by X-ray diffraction using a CCD camera in order to detect reflections of the superstructure building up during the decay. No signal above the noise of the CCD camera was observed, so that even diffuse scattering could not be detected. This finding is in agreement with correlation lengths of pair correlations of molecules in the HS and LS states being very short, as was concluded earlier from the shape of the decay curves of the HS fraction by theoretical considerations [Romstedt et al. (1998). J. Phys. Chem. Solids, 59, 265–275]. The crystal structure inside the step at 118 K has also been studied under continuous irradiation. The temperature range of the superstructure and the degree of order could be changed by continuous irradiation with green laser light, indicating an increase of the lifetime of the HS excited state by several orders of magnitude compared with the temperature regions outside.

The conversion of the spin state of complexes exhibiting thermal spin crossover from the1A1low-spin (LS) state to the5T2high-spin (HS) state is accompanied by a deformation of the lattice due to the larger bond lengths in the HS state as compared with the LS state. In a previous work [Kuszet al.(2000).J. Appl. Cryst.33, 201–205], it has been shown that the deformation of the lattice, corrected for its temperature dependence, can be described by an almost temperature-independent tensor ∊ multiplied by the fraction of molecules in the HS state, γHS. Here the dependence of ∊ in a mixed single crystal of [Fe0.46Zn0.54(ptz)6](BF4)2(ptz = propyltetrazole) with a transition temperature near 110 K is reported. In order to study the dependence of the metal–ligand bond length on the concentration of Zn, five structures were determined at 10 K: the neat iron and the mixed-crystal compound in both the excited HS state (LIESST) and the LS state, and the neat Zn compound. The comparison of the structures shows that neither the bond lengths nor their differences in the HS and LS states depend linearly on the Zn concentration. These deviations can be considered as consequences of elastic interactions directly observed by X-ray diffraction analysis. The lattice constantsaandcalso do not depend linearly on the Zn concentration, contrary to the unit-cell volume and the differences ofaandcbetween the HS and LS states, a fact which is in agreement with the observed linear dependence of these parameters on the temperature-dependent HS fraction.

The effect of hydrostatic pressure on the transition temperature and the hysteresis widths of first-order spin crossover phase transitions is considered in the frame of the mean field theory and on the basis of the scope of recent pressure experiments. Relevant parameters for a qualitative description of the behaviour of spin transition compounds under pressure are derived and analysed.

So far there has been no direct method to determine the spin state of molecules in dinuclear iron(II) compounds. The molecular fractions of high spin (HS) and low spin (LS) species have been deduced from magnetic susceptibility and zero field Mossbauer spectroscopy data irrespective of whether they belong to LS-LS, LS-HS and HS-HS pairs. However, the distinction of pairs becomes possible if Mossbauer measurements are carried out in an external magnetic field. The proposed method opens new possibilities in the study of spin crossover phenomena in dinuclear compounds.

Synchrotron Mossbauer Reflectometry (SMR), the grazing incidence nuclear resonant scattering of synchrotron radiation, can be applied to perform depth-selective phase analysis and to determine the isotopic and magnetic structure of thin films and multilayers. Principles and methodological aspects of SMR are briefly reviewed. Off-specular SMR provides information from the lateral structure of multilayers. In anti-ferromagneticly coupled systems the size of magnetic domains can be measured.

So far there has been no direct method to determine the spin state of molecules in dinuclear iron(II) compounds. The molecular fractions of high-spin (HS) and low-spin (LS) species have been deduced from magnetic susceptibility and zero-field Mossbauer spectroscopy data irrespective of whether they belong to LS–LS, LS–HS and HS–HS pairs. However, the distinction of pairs becomes possible if Mossbauer measurements are carried out in an external magnetic field. The proposed method opens new possibilities in the study of spin crossover phenomena in dinuclear compounds.

Iron(II) complexes exhibiting thermal spin-crossover may be converted from the1A1low-spin (LS) state to the5T2high-spin (HS) state by irradiation with green light (light-induced excited spin-state trapping, LIESST) and from the LS to the HS state by irradiation with red light (reverse LIESST). The lifetime of the metastable LIESST states may be sufficiently long to enable an X-ray diffraction study. The lattice parameters of a single crystal of [Fe(mtz)6](BF4)2(mtz = methyltetrazole) (space groupP21/n) were measured between 300 and 10 K. While one Fe lattice site (A) of the crystal changes from the HS to the LS state near 78 K, the other site (B) remains in the LS state. Using the green light (514 nm) of an argon ion laser the crystal was quantitatively converted to the HS state at 10 K. Irradiation of the crystal at 10 K by red light of a laser diode (820 nm) with siteAin the LS and siteBin the HS state converts siteBalmost completely to the LS state. The lattice parameters of both metastable states were measured up to 50 K, where they start to decay on a minute timescale. At 10 K, a full data set for evaluation of the crystal structure was recorded. The volume change of the crystal per complex molecule accompanying the spin transition is 31.5 Å3at siteAand close to zero [−0.21 (14) Å3] at siteB.

An anomalous spectral doublet attributed to Fe 2+ impurity pairs is observed in Mossbauer absorption spectra of 57 Fe 0.01 Zn 0.99 Se below room temperature. In Mossbauer emission experiments, ZnSe: 57 Co polycrystal and powder sources exhibit below 45 K the nucleogenic Fe 1+ valence state born as an after effect of the electron-capture decay of 57 Co. Above 8 K, the proportion of the nucleogenic Fe 1+ decreases under the effect of the thermally activated Fe 1+ →Fe 2+ relaxation. The activation energy is estimated to 0.004 eV. While nucleogenic Fe 1+ is absent in ZnSe: 57 Co single crystal spectra, increasing proportions are detected in samples with an enhanced specific surface. The formation model of the nucleogenic Fe 1+ is extended to other zinc chalcogenides and a tentative model is developed, which shows the role of the surface electric field in limiting the formation of nucleogenic Fe 1+ in well crystallised source samples.

Using the general approach of Lax for multiple scattering of waves a 2x2 covariant expression for the reflectivity of polarized slow neutrons of a magnetic layer structure of arbitrary complexity is given including polarization effects of the external magnetic field. The present formalism is identical to the earlier published one for the (nuclear) resonant X-ray (Mossbauer) reflectivity and properly takes the effect of the external magnetic field of arbitrary direction on the neutron beam into account. The form of the reflectivity matrix allows for an efficient numerical calculation., 4 pages, no figures, PNCMI2000 - Proceeding of the Third International Workshop on Polarized Neutrons

The valence states of the nucleogenic 57Fe arising from the nuclear disintegration of radioactive 57Co by electron capture decay, 57Co(EC)57Fe, have been studied by Mossbauer emission spectroscopy (MES) in the 57Co-labeled systems: [57Co/Co(terpy)2]Cl2·5H2O (1), [57Co/Co(terpy)2](ClO4)2·1/2H2O (2), and [57Co/Mn(terpy)2](ClO4)2· 1/2H2O (3) (terpy = 2,2‘:6‘,2‘ ‘-terpyridine). The compounds 1, 2, and 3 were labeled with ca. 1 mCi of 57Co and were used as the Mossbauer sources at variable temperatures between 300 K and ca. 4 K. [Fe(terpy)2]X2 is a diamagnetic low-spin (LS) complex, independent of the nature of the anion X, while [Co(terpy)2]X2 complexes show gradual spin transition as the temperature is varied. The Co(II) ion in 1 “feels” a somewhat stronger ligand field than that in 2; as a result, 83% of 1 stays in the LS state at 321 K, while in 2 the high-spin (HS) state dominates at 320 K and converts gradually to the LS state with a transition temperature of T1/2 ≈ 180 K. Variable-temperature Mossbauer...

Iron(II) complexes exhibiting thermal spin crossover may be converted from the1A1low-spin (LS) state to the5T2high-spin (HS) state by irradiation with green light (light-induced excited spin-state trapping, LIESST). The lifetime of the metastable LIESST state may be sufficiently long for X-ray diffraction study. The lattice parameters of a single crystal of [Fe(ptz)6](BF4)2(ptz = propyltetrazole) were measured between 300 and 10 K, while the crystal changed from the HS to the LS state near 135 K. Using the green light (514 nm) of an argon-ion laser, the crystal was quantitatively converted to the metastable LIESST state at 10 K; its lattice parameters were measured up to 50 K, at which point the LIESST state begins to decay on a minute timescale. The change of the lattice parameters can be interpreted by a superposition of a normal temperature dependence, for which the isostructural zinc compound served as a reference, and an almost temperature-independent part which is proportional to the fraction of molecules in the HS state.

Mossbauer emission spectra of a 57Co:ZnSe powder source at low temperature exhibit the overcompensated Fe1+ state of the nucleogenic daughter ion generated as an after effect of the 57Co(EC)57Fe decay. We analyse to what extent the model of competing acceptors is able to account for the formation and fraction of Fe1+ and present evidence for the role of hole trapping by zinc vacancies.

The compound [Fe(phy)2](BF4)2 (phy = 1,10-phenanthroline-2-carbaldehyde phenylhydrazone) shows spin-transition with a hysteresis of 10 K width around room temperature. Continuous irradiation of the compound during heating and cooling with green light (514 nm) shifts the hysteresis in temperature.

Grazing incidence nuclear resonant scattering of synchrotron radiation can be applied to perform depth-selective phase analysis and to determine the isotopic and magnetic structure of thin films and multilayers. Principles and recent experiments of this new kind of reflectometry are briefly reviewed. Methodological aspects are discussed. Model calculations demonstrate how the orientations of the sublattice magnetisation in ferro- and antiferromagnetic multilayers affect time-integral and time-differential spectra. Experimental examples show the efficiency of the method in investigating finite-stacking, in-plane and out-of-plane anisotropy and spin-flop effects in magnetic multilayers.

57Co Mossbauer emission spectra of undoped and Fe or Mg melt-doped LiNbO3 single crystals show substantial amounts of the nucleogenic Fe3+ charge state (*Fe3+) which was generated as an after-effect of the electron-capture of 57Co2+. The proportion of *Fe3+ is markedly dependent on the Mg content and on the stoichiometry of the sample. Electron trapping is described within the model of competing acceptors. The capabilities of the model are investigated in defect structure analysis and charge trapping studies of LiNbO3.

In iron(II) spin-crossover compounds, the transition from the 1A1 low-spin state at low temperatures to the 5T2 high-spin state at elevated temperatures is accompanied by a large increase in metal-ligand bond lengths. The resulting elastic interactions may be pictured as an internal pressure which is proportional to the concentration of the low-spin species. Because pressure stabilises the low-spin state relative to the high-spin state this results in a positive feedback. Thermal transition curves in neat iron(II) spin-crossover compounds are thus invariable much steeper than in diluted mixed crystals, and the high-spin→low-spin relaxation following the light-induced population of the high-spin state at low temperatures is self-accelerating. Strong interactions give rise to a thermal hysteresis, and light-induced bistabilities may be observed for compounds with initially a high-spin ground state and the potential for a light-induced population of the low-spin state. For such compounds, the increasing internal pressure may stabilise the low-spin state sufficiently so that it becomes the molecular ground state above some critical light-induced low-spin fraction. Secondary effects of the elastic interactions include crystallographic phase transitions, inhomogeneous distributions of sites, and anomalies such as steps in the transition curve.

Fast electron trapping processes and aliovalent charge states following the 57Co(EC)57Fe decay are studied in undoped, 5.4 mol% Mg-doped and 0.1 mol% Fe-doped LiNbO3 in various thermochemical reduction (TCR) states. Static 57Co Mossbauer emission spectra of congruent Mg:LiNbO3 recorded at T = 4.2 K in external magnetic field of 4.6 T are presented. Trapping cross section ratios are derived for Fe3+Li, Nb5+Li and Mg2+Li. A method to determine trap concentrations for TCR states of LiNbO3 is outlined. The electron-capture distance of the traps is found to be 2.7±1.4 nm. As this is much smaller than the 6 keV Auger-electron penetration depth, it is concluded that the distribution of the aliovalent charge states at 4.2 K is determined mainly by the 600 eV Auger electrons.

The effect of hydrostatic pressure on the transition temperature and the hysteresis widths of first order spin crossover phase transitions has been studied. A decrease as well as an increase of the hysteresis width with increasing pressure was reported in the literature. The increase of width with increasing pressure contradicts the expectation derived from mean field theory. We remeasured the pressure dependence of the temperature hysteresis of the compound [Fe(phy)2](BF4)2 (phy=1, 10-phenanthroline-2-carbaldehydephenylhydrazone). The spin transition temperatures at ambient temperature are T ↑ 1/2 =289±1 K, T ↓ 1/2 =283±1 K . An increase of the hysteresis width of d Δ T 1/2 / d p=0.29 K kbar −1 up to p=4.1 kbar has been measured confirming the reported anomaly. The change of the average temperatures T1/2=1/2(T↑1/2+T↓1/2) at which the high spin fraction γ is 1/2 is determined to be 3.0±0.2 K kbar−1. Allowing for a pressure dependence of the bulk modulus of the compound, the anomalous increase of hysteresis width can be interpreted.

A thermodynamic description of high spin (HS)⇌low spin (LS) transition curves beyond the Bragg–Williams approximation is given using the Kikuchi cluster variation method (CVM). Transition curves of unusual behaviour (i.e. two step transition) are reproduced by short range interaction energies which are present in addition to long range elastic interaction between the spin changing molecules. The correlations in the distribution of the spin changing centers can be expressed analytically. They give rise to a reduced mixing entropy which was found experimentally in compounds with two step transitions.

The spin-crossover compound [Fe(pic) 3 ]Cl 2 EtOH (pic = 2-picolylamine) shows an unusual two-step spin transition. This is thought to be caused by specific nearest-neighbour interactions and short-range correlations and requires a theoretical treatment of the elastic interactions between the spin-changing molecules beyond the mean-field approximation. Such short-range correlations also influence the high-spin → low-spin relaxation following the light-induced population of the high-spin state at cryogenic temperatures, leading to characteristic deviations from the predictions of a mean-field treatment. These deviations are directly observable by comparison of the full and unperturbed relaxation curves with curves for which the short-range correlations were destroyed using an appropriate irradiation technique. Monte Carlo simulations including both nearest-neighbour and longrange interactions give a description of the observed relaxation curves which is consistent with the thermal spin equilibrium.

The Lamb-Mossbauer Factor (LMF) of molecular crystals is expected to depend on the electronic molecular states by their different intramolecular vibrational frequencies. Revisiting Mossbauer spectra obtained by time differential Mossbauer 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 Mossbauer 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%.

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 Mossbauer 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.

The Monte Carlo method has been applied to reproduce the two-step spin transition in [FexZn1−x(2-pic)3]Cl2 · EtOH (2-pic = 2-picolylamine). The partition function of the Hamiltonian has been factorized in two parts describing the inner degrees of freedom of the spin transition molecules and the interaction between them. The factorization is equivalent to an effective Hamiltonian which can be mapped on an Ising system in an applied magnetic field. The interaction consists of an infinite range and a short range interaction part. Qualitatively the two-step transition under pressure and the Zn diluted system have been well reproduced with infinite range and the next nearest neighbour interaction of ferromagnetic type and the nearest neighbour interaction of antiferromagnetic type in a simple cubic lattice.

The cooperativity of the thermal spin transition in the Fe(II) spincrossover compound [Fe(ptz)6](BF4)2 (ptz = 1-propyltetrazole) and in isomorphous mixed crystals with the isostructural zinc complex is investigated. From powder X-ray measurements the lattice deformation (tensor e) accompanying the spin transition is determined. For diluted mixed crystals with x 0.44 a first order crystallographic phase transition (R3i → P1i) is observed on cooling, which is triggered by the spin transition and can be suppressed by cooling rapidly. The thermal spin transition is measured with UV/VIS optical absorption spectroscopy on mixed single crystals in the R3i structure. From this metal dilution experiment an interaction constant of 169 cm − 1 for the cooperativity of the spin transition is determined. Furtheron, this interaction constant is calculated on the grounds of elasticity theory: The lattice deformation due to the spin transition is traced back to anisotropic elastic point defects, which directly interact with each other via their stress fields and indirectly via the surface of the elastic crystal by an image pressure. The elastic properties of the crystalline matrix are taken in the isotropic approximation. They are derived from the complete sets of anisotropic elastic constants of the pure iron and zinc compounds, which have been measured previously by Brillouin spectroscopy. The contribution of elastic energy calculated this way is ≃ 80% of the experimental value of the interaction constant, i.e. the cooperativity in crystalline spincrossover compounds is quantitatively of elastic nature.

The [Fe(etz),](BF,), spin-cross-over system (etz = 1-ethyl-1 H-tetrazole) crystallizes in space group P1, with the following lattice constants at 298 K: a 10.419(3), b=15.709(1), c = 18.890(2) A = = 71.223(9), =77.986(10), and = 84.62(1)° V = 2862.0(9) A3 and Z = 3. Two nonequivalent lattice sites, one without (site A) and one with (site B) inversion symmetry, are observed. The population of the two sites nA:nB is 2:l. Iron(II) on site A undergoes a thermal low-spin (LS) high-spin (HS) transition with T1/2I, = 105 K. whereas that on site B remains in the high-spin state down to cryogenic temperatures. Application of external pressure of up to 1200 bar between 200 and 60 K does not cause formation of the low-spin state on site B. On site A the high-spin state can be populated as a metastable state at 20 K by irradiating the sample with = 514.5 nm; on site B a light-induced population of the low-spin state can be achieved with = 820 nm.

The theory of both transmission and grazing incidence M\"ossbauer spectroscopy is re-analyzed. Starting with the nuclear susceptibility tensor a common concise first order perturbation formulation is given by introducing the forward scattering amplitude into an anisotropic optical scheme. Formulae of Blume and Kistner as well as those of Andreeva are re-derived for the forward scattering and grazing incidence geometries, respectively. Limitations of several previously intuitively introduced approximations are pointed out. The grazing incidence integral propagation matrices are written in a form built up from 2x2 matrix exponentials which is particularly suitable for numerical calculations and practical fitting of both energy domain (conventional source experiment) and time domain (synchrotron radiation experiment) M\"ossbauer spectra., Comment: 7 pages

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-Mossbauer 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 Gruneisen 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 Mossbauer area data is discussed.

The accidental coincidences of a measuring system based on time-to-amplitude conversion are considered in some detail for the case of low starting and high stopping rates. Two types of accidental coincidences are distinguished, those carrying time information and those without time information. Neglecting any deadtime effects of the detectors, analytical expressions for the calculation of the time distribution of the random coincidences are evaluated. The analytical expressions have been confirmed by Monte Carlo simulations. The procedure is applied to time-differential Mossbauer spectroscopy in order to extract the time spectra of true coincidences. The measured spectrum in a time channel turns out to be a superposition of the true spectrum (true coincidences), a time integral spectrum (random coincidences), and a weighted superposition of true spectra of other time channels (random but time carrying information). A measurement with a single line 57 Co/Rh-source and single line K[Fe(CN) 6 ]·3H 2 O-absorber with stopping rates of 1 MBq shows agreement between the theoretical time-filtered spectra and the corrected measured spectra of true coincidences.

The spin crossover transition curve of the compound (Fe(BPTN)(NCS)2) (BPTN=N,N'-bis(2-pyridylmethyl)-1,3-propanediamine) was measured by Mossbauer spectroscopy and susceptibility measurements. The compound was prepared by two different methods yielding a fine powder (a) and single crystals of approximately 0.5 mm in size (b). The transition temperatures T1/2 of the gradual transitions are 182 K (a) and 186 K (b). Within experimental accuracy the transition curves derived from the fractional absorption areas of the Mossbauer spectra are the same as derived from susceptibility measurements so that there is no indication for different Lamb Mossbauer factors of the high-spin (HS) and low-spin (LS) states as reported in the literature. The observation of quite different Debye temperatures Theta D at temperatures where the compounds are completely converted to the HS and LS state is discussed.

Fe(II) spin-crossover systems can be quantitatively converted from the low-spin (LS) to the high-spin (HS) state well below the thermal transition temperature by irradiating either into the metal-ligand charge transfer or d-d absorption bands, and even in low-spin systems a transient population of the HS state can be achieved. This fact can be made use of to determine HS → LS relaxation rate constants for a wide variety of Fe(II) spin-crossover and low-spin systems. The HS → LS relaxation shows strong deviations from an Arrhenius behaviour, with nearly temperature-independent tunnelling below ∼70 K and a thermally activated process above ∼100 K. The range of more than 12 orders of magnitude in the low temperature tunnelling rate constant can be understood in terms of a non-adiabatic multiphonon process, where in the strong vibronic coupling limit an inverse energy gap law holds.

The Lamb-Mossbauer factor in spin crossover compounds has been the subject of controversial discussions in the literature. For several compounds, a significantly larger Lamb-Mossbauer factor for the complex molecules in the low-spin (fls) than in the high-spin (fhs) state has been reported, while for compounds studied in our laboratory such differences could not be observed. We prepared the compound Fe(tpa)(NCS)2, thef factors of which were reported to be very different. We could not prove thef factors of this compound to be different. The implications of a different structural phase of compound prepared by us are discussed.

The time integral Mossbauer emission spectrum of a57Co/Co1−xO source (x ≈ 10−5) at RT consists of two single Lorentzian lines of an Fe2+ (76%) charge state and an Fe3+ (24%) aliovalent charge state. The spectrum measured by γ-X-ray coincidence spectrpscopy shows the same fraction of the aliovalent charge state, contrary to the expectation derived from the competing acceptor model as successfully applied by Tejada and Parak [1], who could explain the dependence of the formation of aliovalent charge states after the nuclear transformation on the stoichiometric parameterx. The consequences of this unexpected behaviour for the competing acceptor model are discussed.

The Mossbauer emission spectra of nucleogenic iron(II) complexes with a low spin (LS) ground state show two metastable iron(II) high spin (HS) states at low temperatures. In order to identify these metastable HS states, the compound [57Co/Mn(bipyridine)3](PF6)2 has been studied by time differential Mossbauer emission spectroscopy (TDMES) and optical lifetime measurements of excited electronic states in the corresponding Fe-doped Mn compound. The lifetime of one of the HS states of the nucleogenic iron(II) determined by TDMES has been measured to be the same as the lifetime of the laser-excited iron(II) electronic state.

Transition metal chemistry contains a class of complex compounds for which the spin state of the central atom changes from high spin to low spin when the temperature is lowered. This is accompanied by changes of the magnetic and optical properties that make the thermally induced spin transition (also called spin crossover) easy to follow. The phenomenon is found in the solid state as well as in solution. Amongst this class, iron(II) spin crossover compounds are distinguished for their great variety of spin transition behavior; it can be anything from gradual to abrupt, stepwise, or with hysteresis effects. Many examples have been thoroughly studied by Mössbauer and optical spectroscopy, measurements of the magnetic susceptibilities and the heat capacities, as well as crystal structure analysis. Cooperative interactions between the complex molecules can be satisfactorily explained from changes in the elastic properties during the spin transition, that is, from changes in molecular structure and volume. Our investigations of iron(II) spin crossover compounds have shown that green light will switch the low spin state to the high spin state, which then can have a virtually unlimited lifetime at low temperatures (this phenomenom is termed light-induced excited spin state trapping - acronym: LIESST). Red light will switch the metastable high spin state back to the low spin state. We have elucidated the mechanism of the LIESST effect and studied the deactivation kinetics in detail. It is now well understood within the theoretical context of radiationless transitions. Applications of the LIESST effect in optical information technology can be envisaged.

In der Ubergangsmetallchemie gibt es eine Klasse von Komplexverbindungen, bei denen eine Temperaturerniedrigung einen Wechsel im Spinzustand des Zentralatoms vom High-Spin- in den Low-Spin-Zustand bewirkt. Dabei andern sich die magnetischen und optischen Eigenschaften, uber die der thermische Spinubergang (auch Spincrossover genannt) sehr gut verfolgt werden kann. Dieses Phanomen tritt sowohl in flussiger Phase als auch im Festkorper auf. Eine herausragende Stellung nehmen Eisen(II) - Spincrossover - Verbindungen ein, in denen der Spinubergang im Festkorper auf sehr unterschiedliche Weise - graduell, abrupt, mit Hysterese oder stufenweise - verlaufen kann und mit Mosbauer- und optischer Spektroskopie, mit magnetischen Suszeptibilitats- und Warmekapazitatsmessungen sowie durch Kristallstrukturanalyse intensiv untersucht worden ist. Die kooperative Wechselwirkung zwischen den einzelnen Komplexmolekulen kann befriedigend durch elastische Eigenschaften und durch die Anderung von Gestalt und Volumen der Komplexmolekule beim Spinubergang erklart werden. Bei Untersuchungen an Eisen(II)-Spincrossover-Verbindungen konnte man beobachten, das sich der Low-Spin-Zustand mit grunem Licht in den High-Spin-Zustand umschalten last, der bei tiefen Temperaturen eine nahezu unendlich lange Lebensdauer haben kann (LIESST = Light-Induced Excited Spin State Trapping). Mit rotem Licht last sich der metastabile High-Spin- wieder in den Low-Spin-Zustand zuruckschalten. Der Mechanismus des LIESST-Effekts ist aufgeklart, die Zerfallskinetik im Detail untersucht und im Rahmen der Theorie strahlungsloser Ubergange verstanden. Anwendungen des LIESST-Effekts in der optischen Informationstechnik sind denkbar.

Increasing attention is being paid to non-conventional Mossbauer methods in view of the extension of Mossbauer Spectroscopy (MS) to a broadening field of applications. With such long-lasting experiments the shortening of the measuring time required for a given statistical significance is of major practical importance. It is shown that the statistical utility rateu allows one to determine which experimental parameters have a primary role, and it also enables sucessive optimization. It is pointed out for various MS measurements that the strategy for improving the experimental performance is strongly dependent on the given problem. As examples, time-differential Mossbauer measurements and conversion electron Mossbauer spectroscopy are discussed.

With a new type of calorimeter we reinvestigated the specific heat Cp of the mixed crystals [FexZni1−x(2-pic)3]Cl2 · EtOH in the temperature range from 15 to 300 K. On the basis of a phenomenological thermodynamic model the anomaly in the Cp(T) curve of the mixed crystal (x = 0.73) can be quantitatively described as a result of the spin transition (1A1(low spin, LS) → 5T2(high spin, HS)). The parameters of the Gibbs free energy were independently derived from the temperature dependence of the HS fraction γ in [FexZn1−x(2-pic)3]Cl2 · EtOH. The pure iron complex (x = 1) exhibits a two-step spin transition. In the temperature range between the two steps the entropy obtained from the Cp values is lower than expected from a random mixture of HS and LS complexes in the crystal. This reduction of entropy is interpreted in terms of an ordering of HS and LS molecules.

Exquisite sensitivity of Mossbauer spectroscopy for tiny local molecular distortion is demonstrated in [FeII2(pmat)2](BF4)4?DMF: high-spin (HS) iron(II) in [HS-HS] and in [LS-HS] (low-spin–high-spin) pairs is clearly distinguished (see picture) for the first time without the need to apply a magnetic field. This dinuclear complex clearly shows that spin crossover via a [LS-HS] species is promoted by the use of a highly constrained bridging ligand (the bis-terdentate pmat).

After effects following nuclear transformation have been extensively studied in a large variety of matrices by Mossbauer Emission Spectroscopy (MES). The branching ratios of transient atomic charge states and energetically unstable states of the environment, excitations of electronic ligand field states and populations out of equilibrium within the electronic ground state manifold have been studied. Recent developments and also new insights and understandings of different aspects of the aftereffects of radioactive decay of57Co in semiconductors and molecular crystals are reviewed. A detailed picture of the decay process within the electronic states of the nucleogenic Fe3+ species could be obtained from emission spectroscopy of sources in applied magnetic fields.

Using our new spectrometer for time-differential Mossbauer emission spectroscopy we reinvestigated the high-spin→low-spin relaxation following the57Co(EC)57Fe process in [57Co/Co(phen)3](ClO4)2 (phen=1,10-phenanthroline). In contrast to former investigations we found a temperature dependent initial population less than 1 for the metastable high-spin states. The results and the data evaluation method are presented.

Results on the incorporation, valence and spin states of Fe(Co) in CuO (with reference to similar studies on high temperature superconductors) and coupling of the Fe(Co) moment to the Cu magnetism in CuO are presented. Freshly prepared57Co: CuO shows two quadrupole doublets D1 and D2 withQ.S. of 2.49 and 1.52,I.S. of 0.35 and 0.70 mm/s and relative abundance of 74% and 26%, respectively at room temperature, the abundance being dependent on time in a sample exposed to ambient conditions and reaching 38 to 62% fifteen months after preparation. Below,TN=2251K, a typical combined magnetic-quadrupole interaction pattern is observed with a single saturation magnetic hfs of 25.6 T, central shift of 0.82 mm/s and a single |EQ|=1.62 mm/s at 4.2 K. External magnetic field spectra reveal an antiferromagnetic behaviour of the Fe(Co) ion. Temperature dependence of the magnetic hfs is fitted in the framework of the molecular field approximation allowing different spins and coupling constants for Cu and Fe(Co).

The thermal and light-induced high-spin (HS: 5T2g) low-spin (LS: 1A1g) transitions of [Fe(ptz)6](BF4)2 (ptz = 1-propyltetrazole) are investigated by X-ray powder diffractometry in the range between ambient temperature and ~15 K. The anisotropic lattice deformation caused by variation of the HS fraction and by temperature change was calculated directly from the differences in peak positions of the powder diagrams measured at different temperatures. An analytical expression for the dependence of peak shifts and splittings on the deformation tensor elements was derived. The differences of the lattice deformations accompanying the thermal and light-induced spin transitions are discussed.

Starting from the phenomenological free energy describing the spin equilibrium of continuous or gradual high spin (HS) ⇌ low spin (LS) transitions a reduced equation of state has been derived which is of the type known in mean field theories. The continuous HS ⇌ LS transitions of [Fe(2-pic-ND 2 ) 3 ]Cl 2 ·EtOD (2-pic = 2-picolylamine) at ambient pressure and p = 1200 bar and of [Fe(2-pic) 3 ]Cl 2 -MeOH can be classified as isobars above the critical point of the system. Around and below the critical point a complex behaviour is expected for thermodynamic reasons combined with the consequences of an elastic interaction mechanism between the HS and LS complex molecules in the crystal. The unusual spin transitions of [Fe x Zn 1 − x (2-pic) 3 ]Cl 2 ·EtOH (two-step transition x ~1) and of [Fe(2-pic) 3 ]Br 2 -EtOH (narrow hysteresis only in the upper part of the transition curve) have been shown to be below and close to above the critical point, respectively. Results from Mossbauer and susceptibility studies of the two-step transition at different concentrations, x = 1.0, 0.98, 0.94, 0.89, 0.86, 0.78 and applied pressures of p = 600 and 1350 bar are strong evidence for the intrinsic properties of the interaction mechanism being responsible for the observed complex behaviour rather than special lattice properties serving as triggers. Static density waves of the HS fraction in the transition region as observed for hydrogen in metal systems, are suggested to be responsible for the observed complex behaviour.

Theoretical description of off-specular grazing-incidence nuclear resonant scattering of synchrotron radiation (Synchrotron M\"{o}ssbauer Reflectometry, SMR) is presented. The recently developed SMR, similarly to polarized neutron reflectometry (PNR), is an analytical tool for the determination of isotopic and magnetic structure of thin films and multilayers. It combines the sensitivity of M\"{o}ssbauer spectroscopy to hyperfine interactions and the depth selectivity of x-ray reflectometry. Specular reflection provides information on the depth profile, while off-specular scattering on the lateral structure of scattering layers. Off-specular SMR and PNR intensity formulae of a rather general multilayer with different domains, based on a Distorted Incident-Wave Approximation (DIWA) are presented. The Distorted-Wave Born Approximation (DWBA) results are given in an Appendix. Physical and numerical implications, why using DIWA, are explained. The temporal character of SMR imposes specific differences between SMR and PNR. In order to reveal the limits of DIWA and to compare the two analytical methods, two-dimensional diffuse SMR and PNR maps of an antiferromagnetic multilayer are calculated and critically compared. Experimental '$\omega-2\theta$' SMR map of a periodic $[ \mathrm{Fe}/\mathrm{Cr}]_{20}$ multilayer is presented and compared with simulations by the present theory., Comment: 6 figures, submitted to PRB

This review reports on the study of the interplay between magnetic coupling and spin transition in 2,2'-bipyrimidine (bpym)-bridged iron(II) dinuclear compounds. The coexistence of both phenomena has been observed in {[Fe(bpym)(NCS) 2 ] 2 (bpym)}, {[Fe(bpym)(NCSe) 2 ] 2 (bpym)} and {[Fe(bt)(NCS) 2 ] 2 (bpym)} (bpym=2,2'-bipyrimidine, bt = 2,2'-bithiazoline) by the action of external physical perturbations such as heat, pressure or electromagnetic radiation. The competition between magnetic exchange and spin crossover has been studied in {[Fe(bpym)(NCS) 2 ] 2 (bpym)} at 0.63 GPa. LIESST experiments carried out on {[Fe(bpym)(NCSe) 2 ] 2 (bpym)}and {[Fe(bt)(NCS) 2 ] 2 (bpym)}at 4.2 K have shown that it is possible to generate dinuclear molecules with different spin states in this class of compounds. A special feature of the spin crossover process in the dinuclear compounds studied so far is the plateau in the spin transition curve. Up to now, it has not been possible to explore with a microscopic physical method the nature of the species which constitute such a plateau, due to the relatively high temperatures at which the transition takes place. A two-step spin transition has been -observed for {[Fe(phdia)2(NCS) 2 ] 2 (Phdia)} (phdia: 4,7-phenanthroline-5,6-diamine) with T 1 / 2 (1) and T 1 / 2 (2) located at 108 and 80 K, respectively. Due to this low temperature transition we were able to thermally trap, at liquid helium temperatures, the species present in the plateau of the spin transition curve. The results have revealed that the plateau consists mainly of [HS-LS] pairs, and they confirmed the hypothesis formulated earlier that the spin conversion in dinuclear entities proceeds via [HS-HS]↔[HS-LS]↔[LS-LS] pairs.