High-spin → low-spin relaxation in the two-step spincrossover compound [Fe(pic)3]Cl2EtOH (pic = 2-picolylamine)

Abstract 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 unperturb…

Pressure effect on temperature induced high-spin–low-spin phase transitions

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.

Interplay of Antiferromagnetic Coupling and Spin Crossover in Dinuclear Iron(II) Complexes

This article reports on the study of the interplay between magnetic coupling and spin transition in 2,2′-bipyrimidine (bpym)-bridged iron(II) dinuclear compounds. Coexistence of both phenomena has been observed in [Fe(bpym)(NCS)2]2bpym, [Fe(bpym)(NCSe)2]2bpym and [Fe(bt)(NCS)2]2bpym (bpym = 2,2′-bipyrimidine, bt = 2,2′-bithiazoline) by the action of external physical factors namely pressure or electromagnetic radiation. Competition between magnetic exchange and spin crossover has been studied in [Fe(bpym)(NCS)2]2bpym at 6.3 kbar. LIESST experiments carried out in [Fe(bpym)(NCSe)2]2bpym and [Fe(bt)(NCS)2]2bpym at 4.2 K have shown that is possible to achieve dinuclear molecules with different…

Helium gas pressure cell for pressures up to 1 kbar (0.1 GPa) in conjunction with the cold head of a closed-cycle He refrigerator

A helium gas pressure cell for pressures up to 1 kbar (0.1 GPa) has been developed in conjunction with a closed-cycle He refrigerator allowing variable temperatures between 15 and 300 K. Both cell and refrigerator are equipped with optical windows suitable for photophysical measurements, such as temperature- and pressure-dependent absorption spectroscopy or laser flash photolysis. Examples of measurements on iron(II) spin-crossover systems are given. In these compounds, comparatively small external pressures induce significant changes in the thermodynamic equilibrium as well as in the relaxation dynamics.

High-performance Mössbauer spectroscopy: Criteria, possibilities, limitations

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 conv…

Thermodynamics of the spin transition in [FexZn1−x(2-pic)3]Cl2 · EtOH

Abstract 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 C…

Anomalous pressure dependence of the Lamb-Mössbauer factor in a spin crossover system

The dependence of the f-factor on temperature and on pressure up to 1500 bar has been measured in the spin crossover compound [Fe(2-pic-ND2)3]cl2·EtOD. In the transition region around Tc=146.7 K the pressure dependence of f shows an anomalous increase, which can be explained on the basis of a theoretical model for spin transitions developed by us.

Spin crossover behavior under pressure of Fe(PM-L)2(NCS)2 compounds with substituted 2′-pyridylmethylene 4-anilino ligands

Abstract New iron(II) spin crossover systems with large aromatic ligands, based on 2′-pyridylmethylene 4-anilino units, have been synthesized and studied. The whole range of spin crossover behavior has been observed, starting from pure high-spin to more or less complete gradual transitions and finally to discontinuous type transitions with both small and large hysteresis. Magnetic measurements under pressure have revealed that two of the compounds exhibit pressure-induced new phases with larger hysteresis than at atmospheric pressure. For one of the compounds the formation of this new phase is irreversible and the hysteresis width is ∼100 K, as compared to 37 K before applying pressure.

Strong Field Iron(II) Complex Converted by Light into a Long-Lived High-Spin State

LIGAND FIELD CALCULATION FOR THE COMPLEX Fe(H2O)2+6 IN FROZEN AQUEOUS SOLUTION OF Fe(ClO4)2

Intersystem crossing in Fe(II) coordination compounds

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…

Time integral and time differential Mössbauer measurements on [57Co/Mn(bipy)3](PF6)2

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.

Correlations of the distribution of spin states in spin crossover compounds

Abstract Short range correlations of the distribution of high spin (HS) and low spin (LS) states show up in thermal spin transition curves, decay curves of the light induced metastable HS state (LIESST state), and in structural features during the spin transitions. Correlations are due to short range interactions between the spin crossover molecules. Short range interactions may compete with omnipresent long range interactions and give rise to interesting spin transition phenomena. In this paper, the effect of correlations on the thermal spin transition in the mixed crystal system [Fe x Zn 1− x (pic) 3 ]Cl 2 ·EtOH (pic=picolylamine) is discussed. In particular the step in the thermal transi…

The LIESST state of [Fe(pic)3]Cl2.EtOH – the superstructure under continuous irradiation

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 bei…

Time-differential Mössbauer emission spectroscopy: Development of a new spectrometer and first results

A spectrometer for time-differential Mossbauer spectroscopy was developed with a high count rate capability, a good time resolution, and a flexible data handling. Chemical and physical aftereffects following the57Co decay were studied within the cobalt doped systems Turnbulls blue and ZnS.

Light-Induced Excited Spin State Trapping in Iron(II) Complexes

In the course of our studies on the thermally induced high spin (HS) ↔ low spin (LS) transition in iron(II) complexes /1/, \({\!^5{\text{T}}_2}_{\text{g}}\) ↔ \({\!^1{\text{A}}_1}_{\text{g}}\) in the approximation of Oh symmetry, we have observed in 1984 a new photophysical effect /2/: If, at sufficiently low temperature, the solid spin crossover complex is irradiated with green light into the \({\!^1{\text{A}}_1}\)→ \({\!^1{\text{T}}_1}\) ligand field absorption band, the thermodynamically stable LS state can be converted to the metastable HS state and trapped with practically infinite lifetime. We have called this unusual phenomenon “Light-Induced Excited Spin State Trapping (LIESST)”.

Stark-Feld-Eisen(II)-Komplex konvertiert durch Licht in einen langlebigen High-Spin-Zustand

A common optical algorithm for the evaluation of specular spin polarized neutron and Mössbauer reflectivities

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.

Vibrational spectrum of the spin crossover complex [Fe(phen)(2)(NCS)(2)] studied by IR and Raman spectroscopy, nuclear inelastic scattering and DFT calculations.

The vibrational modes of the low-spin and high-spin isomers of the spin crossover complex [Fe(phen)(2)(NCS)(2)] (phen = 1,10-phenanthroline) have been measured by IR and Raman spectroscopy and by nuclear inelastic scattering. The vibrational frequencies and normal modes and the IR and Raman intensities have been calculated by density functional methods. The vibrational entropy difference between the two isomers, DeltaS(vib), which is--together with the electronic entropy difference DeltaS(el)--the driving force for the spin-transition, has been determined from the measured and from the calculated frequencies. The calculated difference (DeltaS(vib) = 57-70 J mol(-1) K(-1), depending on the m…

The [Fe(etz)6](BF4)2 Spin-Crossover System—Part One: High-Spin ⇌ Low-Spin Transition in Two Lattice Sites

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 for…

Lamb-Mössbauer factor in the spin crossover compound Fe(tpa)(NCS)2

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.

Modelling of two step high spin⇌low spin transitions using the cluster variation method

Abstract 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.

Switching Reciprocity On and Off in a Magneto-Optical X-Ray Scattering Experiment Using Nuclear Resonance ofα−Fe57Foils

Reciprocity is when the scattering amplitude of wave propagation satisfies a symmetry property, connecting a scattering process with an appropriate reversed one. We report on an experiment using nuclear resonance scattering of synchrotron radiation, which demonstrates that magneto-optical materials do not necessarily violate reciprocity. The setting enables us to switch easily between reciprocity and its violation. In the latter case, the exhibited reciprocity violation is orders of magnitude larger than achieved by previous wave scattering experiments.

Dynamics of spin state conversion processes in the solid state

High spin (HS) ⇌ low spin (LS) conversions in transition metal complexes are nonradiative transitions between spin states. In this contribution, we present a study of the temperature and pressure dependence of the HS ⇌ LS intersystem crossing dynamics. For some iron(II) spin-crossover complexes, the rate constants were determined by line shape analysis of57Fe Mossbauer spectra. Their temperature dependence is described by an Arrhenius equation, their pressure dependence is interpreted within absolute rate theory. HS → LS conversion rates at low temperatures were determined from the relaxation of light-induced formation of HS states, monitored by optical spectroscopy. Deviations from a simpl…

The [Fe(etz)6](BF4)2 Spin-Crossover System - Part Two: Hysteresis in the LIESST Regime

In the [Fe(etz)6](BF4)2 spincrossover system the iron(II) complexes occupy two nonequivalent lattice sites, sites A and B. Complexes on site A show a thermal high-spin (HS) low-spin (LS) transition at 105 K, whereas complexes on site B remain in the HS state down to 10 K. Complexes on both sites exhibit light-induced spin state conversions (LIESST) at 20 K: LS HS on site A with = 514.5 nm, and HS LS on site B with = 820 nm. The relaxation processes subsequent to the HS LS conversion on site B reveal a light-induced HSLS bistability for the complexes on site B at 70 K. The bistability as well as the absence of a thermal spin transition on site B are attributed to a thermal hysteresis for the…

Advances in Mössbauer Emission Spectroscopy

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 o…

57Co emission studies of cupric oxide

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 o…

61Ni MÖSSBAUER EFFECT STUDIES OF THE FERRIMAGNETIC SPINEL NiCr2O4 IN AN APPLIED MAGNETIC FIELD

New time-differential Mössbauer emission measurements on the high-spin→low-spin relaxation in [57Co/Co(phen)3](ClO4)2

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.

Electronic Relaxation Phenomena Following 57Co(EC)57Fe Nuclear Decay in [MnII(terpy)2](ClO4)2·1/2H2O and in the Spin Crossover Complexes [CoII(terpy)2]X2·nH2O (X = Cl and ClO4):  A Mössbauer Emission Spectroscopic Study

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 temp…

The debye-waller factor in spincrossover molecular crystals: a mössbauer study on [FexZn1−x(ptz)6](BF4)2

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 anisotro…

Mössbauer relaxation spectra in arbitrarily ordered absorbers—Line shape analysis for an iron(II) spincrossover complex in the presence of texture

The stochastic theory of Mossbauer line shapes is formulated in a fashion which allows the evaluation of the spectral shapes for absorbers of arbitrary thickness, texture, and an anisotropic Lamb—Mossbauer factor. The results are specialized to a two-state-relaxation model of fluctuating electric hyperfine interaction in the case of an absorber of axially symmetric texture. The formalism is applied to the line shape analysis of Mossbauer spectra of a textured sample of the spin-crossover complex [Fe(mtz)6] (PF6)2 (mtz=1-methyltetrazole). It is found that between 185 and 240 K the rate constants for the HS→LS conversion are temperature independent, whereas an Arrhenius behaviour is found for…

Mixed spin-state [HS-LS] pairs in a dinuclear spin-transition complex: confirmation by variable-temperature 57Fe Mössbauer spectroscopy.

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).

The influence of hydrostatic pressure on hysteresis phase transition in spin crossover compounds

Abstract 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=…

Electronic, vibrational, and structural properties of a spin-crossover catecholato-iron system in the solid state: theoretical study of the electronic nature of the doublet and sextet states.

As a functional model of the catechol dioxygenases, [(TPA)Fe(Cat)]BPh4 (TPA = tris(2-pyridylmethyl)amine and Cat = catecholate dianion) exhibits the purple-blue coloration indicative of some charge transfer within the ground state. In contrast to a number of high-spin bioinspired systems, it was previously shown that, in the solid state, [(TPA)Fe(Cat)]BPh4 undergoes a two-step S = 1/2 = S = 5/2 spin-crossover. Therefore, the electronic and vibrational characteristics of this compound were investigated in the solid state by UV/Vis absorption and resonance Raman spectroscopies over the temperature range of the transition. This allowed the charge-transfer transitions of the low-spin (LS) form …

Cooperative pseudo-Jahn-Teller effect of the Fe(H2O)62+complexes in the sulfate heptahydrates

Quadrupole splitting of Fe(II) spin crossover compounds study of temperature and pressure dependence and the implication for the interaction mechanism

The temperature and pressure dependence of the quadrupole splitting ΔE Q of the 3/2→1/2 nuclear Mossbauer transition of57Fe in the spin crossover compounds [Fe x Zn1−x (2-pic)3]Cl2⋆EtOH and the deuterated analog [Fe x Zn1−x (2-pic-ND2)3] Cl2⋆EtOD (2-pic=2-picolylamine) have been studied. The change of ΔE Q can be linearly related to the defomation of the lattice as observed by X-ray measurements. The dependence of ΔE Q on temperatureT, pressurep, and the fraction γ of molecules in the electronic high spin state in the pure iron (x=1) compounds is therefore interpreted as a result of the change of the lattice contribution to the electric field gradient (EFG) at the nucleus only. The intrinsi…

Nature of the phase transition in spin crossover compounds

Abstract 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…

Coarsening of Antiferromagnetic Domains in Multilayers: The Key Role of Magnetocrystalline Anisotropy

The domain structure of an antiferromagnetic superlattice is studied. Synchrotron Mössbauer and polarized neutron reflectometric maps show micrometer-size primary domain formation as the external field decreases from saturation to remanence. A secondary domain state consisting mainly of at least 1 order of magnitude larger domains is created when a small field along the layer magnetizations induces a bulk-spin-flop transition. The domain-size distribution is reproducibly dependent on the magnetic prehistory. The condition for domain coarsening is shown to be the equilibrium of the external field energy with the anisotropy energy.

Titelbild: Mixed Spin-State [HS-LS] Pairs in a Dinuclear Spin-Transition Complex: Confirmation by Variable-Temperature57Fe Mössbauer Spectroscopy (Angew. Chem. 16/2008)

The average over a sphere

Abstract The N points ri and the N segments ΔΩi of the unit sphere used in the numerical approximation of the average over the sphere are optimized to approximate the average of the set of spherical harmonics {;Yl,m;l = 0, 1, 2, …, L}; up to L = 18. The symmetry of f( r ) can be taken into acount by using only a distinct subquantity of the N point {; r i , ΔΩ i }; . Sets for N = 48n (n = 1, 2, …, 6) are tabulated. The advantage of the method is shown by the calculation of a powder Mossbauer spectrum including electric and magnetic hyperfine interactions.

Cooperative phenomena and light-induced bistability in iron(II) spin-crossover compounds

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-…

Mössbauer effect study of the temperature and pressure dependence of the singlet-quintet intersystem crossing dynamics in an iron(II) spin crossover complex

The lineshapes of Mossbauer spectra of the iron(II) spin crossover complex [Fe(6-mepy)3 tren] (PF6)2 are affected by the dynamics of the HS⇌LS equilibrium. The lineshapes are reproduced with a stochastic two-state-relaxation-model yielding rate constants similar to those determined for related complexes in solution. Application of an external pressure of 150 MPa increases the relaxation rate.

X-ray study of the light-induced metastable state of a spin-crossover compound

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 poin…

ChemInform Abstract: Thermoanalytic Investigations on Mixed Crystals of the Spin-Crossover System (FexZn1-x(2-pic-ND2)3)Cl2·EtOD

Recent developments in the evaluation of Mössbauer line intensities

The angular dependence of the intensities of pure or mixed multipole transitions is formulated in a new fashion, which takes into account arbitrary texture of the Mossbauer absorber ranging from complete orientation (single crystals) over preferred orientation to random powders and an anisotropic absorption fraction of the nuclei. The application of the theory is demonstrated by means of typical examples from the literature.

Investigations on the photoelectron conversion efficiency of NaI(Tl) counters

Abstract The photoelectron conversion efficiency of NaI(Tl) detectors has been measured by counting single photoelectron pulses of the detector output pulse train on a very fast storage oscilloscope. This result is compared with those obtained by the measurement of the achievable time resolution using the first photoelectron triggering technique.

Total free energy of a spin-crossover molecular system

The free energy of spin-crossover molecular systems studied so far deal with the inner degrees of freedom of the spin-crossover molecules and a variety of interaction schemes between the molecules in the high spin (HS) and low spin (LS) states. Different types of transition curves, gradual, abrupt, hysteresis, and also two step transitions have been simulated or even satisfactorily fitted to experimental data. However, in the last decade spin transition curves were measured, especially under pressure, which could not be explained within these theoretical models. In this contribution the total free energy of an anharmonic lattice incorporating spin-crossover molecules which have a certain mi…

Comparative Mössbauer spectroscopic study of iron impurities in ZnSe

Abstract 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. Th…

Coherent forward-scattering amplitude in transmission and grazing incidence Mössbauer spectroscopy

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 a…

A time-differential Mössbauer emission spectrometer with high efficiency and high time resolution

A high-efficiency, high rate-capability, computer-based measuring setup for Time-Differential Mossbauer Spectroscopy was constructed. Applying NaI(Tl) and plastic scintillators for the detection of the 14.4 keV and 122 keV γ-radiation respectively, a superior timing (2, 3 ns FWHM) was achieved by a “fast-fast-ultra fast” timing method developed for that purpose.

Cover Picture: Mixed Spin-State [HS-LS] Pairs in a Dinuclear Spin-Transition Complex: Confirmation by Variable-Temperature57Fe Mössbauer Spectroscopy (Angew. Chem. Int. Ed. 16/2008)

Mössbauer Emission Spectroscopy of Mixed-Valency after Nuclear Decay in Iron Complexes

The population of anomalous spin states and aliovalent charge states of iron induced by the 57 Co(EC)57 Fe nuclear decay in polycristalline transition metal compounds was studied by means of Coincidence Mossbauer Emission Spectroscopy (CMES), that is Time-Differential Mossbauer Emission Spectroscopy (TDMES) as well as γ/Xray-Coincidence Mossbauer Emission Spectroscopy (γ/X-CMES). By use of time-integral Mossbauer emission spectroscopy (TIMES) we have observed anomalous high spin (S = 2) states of 57 Fe(II) in the system [57Co/Co(phen)3(ClO 4)2 with increasing intensities on lowering the temperature. With TDMES we followed quantitatively the high spin-low spin relaxation kinetics in this com…

Electron trapping centres and cross sections in LiNbO3studied by57Co Mössbauer emission spectroscopy

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 alioval…

Spin Transition Phenomena

Direct monitoring of spin state in dinuclear iron(II) coordination compounds

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.

The effect of low pressure on a high-spin—low-spin transition

Abstract The effect of low pressure ( p = 150 bar) on the high-spin (HS)—low-spin (LS) transition in [Fe x Zn 1− x (2-pic) 3 ]Cl 2 · EtOH ( x = 0.5, 1.0) was measured by Mossbauer spectroscopy and the results compared with theory. The linear dependence of the volume of the lattice on the HS fraction, which is the basic assumption of the theory, was proven by temperature dependent X-ray measurements.

Stroboscopic detection of nuclear resonance in an arbitrary scattering channel

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 d…

Mössbauer Spectroscopic Evidence of Angle-Dependent Intersystem Crossing in LiNbO3:Fe3+

M\"ossbauer emission spectra of LiNb${\mathrm{O}}_{3}$:$^{57}\mathrm{Co}$ single crystals in magnetic fields up to 5 T at 4.2 K show initial populations of the $^{6}A_{1\mathrm{g}}$ Zeeman substates of ${\mathrm{Fe}}^{3+}$ which depend strongly on the angle between the crystallographic $c$ axis and the magnetic field. This is interpreted in terms of a crystal-field effect on excited states which influences the initial populations of the Zeeman sublevels of the $^{6}A_{1\mathrm{g}}$ ground term after the electron-capture decay of $^{57}\mathrm{Co}$. An intersystem crossing process due to orbit-lattice interaction can fairly well explain the angular dependence.

Light-induced excited spin-state trapping of the Fe(ppi)2(NCS)2 complex

The deformation tensor ∊ of the spin transition in the mixed crystal [Fe0.46Zn0.54(ptz)6](BF4)2

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 …

Realizing total reciprocity violation in the phase for photon scattering

Scientific reports 7, 43114 (2017). doi:10.1038/srep43114

Mössbauer and magnetic studies of mixed-valence linear chain compounds: Na3Fe2S4 and Na3Fe2Se4

Mossbauer and magnetic data establish the two compounds Na3Fe2X4(X=S, Se) as mixed-valence linear chain compounds with rapid valence fluctuation. The compounds exhibit 1-dimensional antiferromagnetic coupling within the chains, and below a critical temperature a 3-dimensional ferrimagnetic ordering between the chains.

Synchrotron Mössbauer Reflectometry in Materials Science

57Fe nuclear resonant scattering experiments are reported on iron-containing thin films using 14.41 keV synchrotron radiation at angles of grazing incidence around and slightly above the critical angle of the electronic total reflection. In partially oxidised α–Fe films of 20 nm original thickness various oxide and oxihydroxide phases are identified at different depth. In a [Fe/FeSi]10multilayer grown on Zerodur®substrate the Fe—Fe interlayer coupling varies with the distance from the substrate. The antiferromagnetic order of the top layers of this multilayer can be suppressed by external magnetic field. These examples demonstrate the efficiency of synchrotron Mossbauer reflectometry (SMR),…

Gamma-X-ray coincidence Mössbauer emission spectroscopy on57Co/CoO

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 Electric Field Gradient and the Quadrupole Interaction

The Mossbauer effect has become a popular method in analytical chemistry. In contrast to other techniques such as x-ray spectroscopy, NMR, EPR, and MCD where highly sophisticated evaluation procedures are applied to obtain reliable information on the chemical compound, the Mossbauer effect is generally used on a low level concerning the evaluation of quadrupole split spectra. This procedure on a low level is favored by the structure of the spectra especially the simple doublet of the 3/2 → 1/2 nuclear transitions in paramagnetic and diamagnetic compounds. The separation of the two absorption lines, the quadrupole splitting ΔE Q and the center of the two lines, the isomer shift, are easily d…

Anomalous pressure dependence of the Lamb-Mössbauerf-factor in the spin crossover system [Fe(2-pic-ND2)3]Cl2·EtOD

The pressure dependence of the Lamb-Mossbauer factor of the spin crossover compound [Fe(2-pic-ND2)3]Cl2·EtOD(2-pic-ND2=2-picolylamine, deuterated at the−NH2 group) has been measured at pressures up to 1500 bar and at three temperatures (115.7, 146.7, 185.6 K) around the transition temperatureT t=135 K. The temperature dependence of the unit cell volume has been determined by X-ray diffraction. In the transition region (T=146.7 K), the pressure dependence of thef-factor shows an anomalous increase as compared to the dependence below and above the transition. The behaviour off(p, T), its anomaly and absolute value, can be consistently explained within a theoretical model which treats the comp…