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 Mössbauer 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—Mössbauer 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 Mössbauer 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 the LS→HS conversion.     

Pressure-induced electron spin transition in the paramagnetic phase of the GdFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> Heisenberg magnet

The HS → LS spin crossover effect (high-spin → low-spin transition) induced by high pressure in the range 45–53 GPa is observed in trivalent Fe³⁺ ions in the paramagnetic phase of a Gd⁵⁷Fe₃(BO₃)₄ gadolinium iron borate crystal. This effect is studied in high-pressure diamond-anvil cells by two experimental methods using synchrotron radiation: nuclear resonant forward scattering (NFS) and Fe K _β high-resolution x-ray emission spectroscopy (XES). The manifestation of the crossover in the paramagnetic phase, which has no order parameter to distinguish between the HS and LS states, correlates with the optical-gap jump and with the insulator-semiconductor transition in the crystal. Based on a theoretical many-electron model, an explanation of this effect at high pressures is proposed.     

Intermediate electronic relaxation betweenS=3/2 andS=1/2 states in Fe(J-mph)NO with a jäger-type ligand J-mph

The incomplete spin transition between the low-spin (LS) (S=1/2) and the intermediate-spin (IS) (S=3/2) states in the iron (III) complex Fe(J-mph)NO (mph=4-methyl-o-phenylene), centered atT _c≈212 K, has been studied with⁵⁷Fe Mössbauer spectroscopy and magnetic susceptibility measurements between 80 K and 320 K. The lineshape of the Mössbauer spectra is well reproduced by a two state stochastic relaxation model resulting in values of about 2·10⁶ s^?1 to 7·10⁶ s^?1 for the IS→LS transition rate constantk _IL. The kinetics of this spin transition can be described by an Arrhenius equation yielding activation energiesE _IL=1.1 (2) kJ/mol andE _LI=6.1 (2) kJ/mol for the IS→LS and LS→IS conversion, respectively.     

Fe（II）-NH(a1Δ)N4S2自旋翻转单分子磁体的电子输运性质

Spin-crossover (SCO) magnets can act as one of the most possible building blocks in molecular spintronics due to their magnetic bistability between the high-spin (HS) and low-spin (LS) states. Here, the electronic structures and transport properties through SCO magnet Fe(II)-N₄S₂ complexes sandwiched between gold electrodes are explored by performing extensive density functional theory calculations combined with non-equilibrium Green''s function formalism. The optimized Fe-N and Fe-S distances and predicted magnetic moment of the SCO magnet Fe(II)-N₄S₂ complexes agree well with the experimental results. The reversed spin transition between the HS and LS states can be realized by visible light irradiation according to the estimated SCO energy barriers. Based on the obtained transport results, we observe nearly perfect spin- filtering effect in this SCO magnet Fe(II)-N₄S₂ junction with the HS state, and the corresponding current under small bias voltage is mainly contributed by the spin-down electrons, which is obviously larger than that of the LS case. Clearly, these theoretical findings suggest that SCO magnet Fe(II)-N₄S₂ complexes hold potential applications in molecular spintronics.     

Hydrostatic pressure driven spin,volume and band gap collapses in SmFeO3: a GGA + U study

The crystal structure, magnetic and electronic properties of SmFeO₃ under hydrostatic pressure have been studied by first-principles calculations within the generalized gradient approximation plus Hubbard U (GGA + U). The iso-structural phase transition with spin, volume and band gap collapses can be induced by a large enough hydrostatic pressure. The high-spin (HS) state of Fe³⁺, with the magnetic moment of ~4 μ_B, is retained at low pressure. The spin crossover occurs at a transition pressure (~68 GPa) with the magnetic moment of Fe³⁺ decreasing to ~1 μ_B in low-spin (LS) state. Meanwhile, the reductions of cell volume (by ~?5.43%) and band gap (from >2 eV to ~1.6 eV) of SmFeO₃ are obtained when the HS–LS transition happens. Finally, the critical pressure of HS–LS transition, magnetic and electronic properties are found to be Hubbard U dependent.     

The spin-crossover complex [Fe(tpa)(NCS) 2 ]

The temperature-induced spin crossover of iron(II) in the [ Fe ( tpa )( NCS ) ₂ ] complex has been investigated by nuclear forward scattering (NFS), nuclear inelastic scattering (NIS), extended X-ray absorption fine structure (EXAFS) spectroscopy, conventional M?ssbauer spectroscopy (MS) and by measurements of the magnetic susceptibility (SQUID). The various measurements consistently show that the transition is complete and abrupt and exhibits a hysteresis between 102 and 110 K. The dependence of the hyperfine parameters of the high-spin (HS) and of the low-spin (LS) phase on temperature is gradual while the effective thickness (determined by the Lamb-M?ssbauer factor f _LM ) shows a step at the transition temperature. This step could be identified clearly because the effective thickness is measured directly by NFS. The Lamb-M?ssbauer factor, the Debye temperature and the mean-square displacement of iron(II) could be determined for the HS and for the LS phase. When comparing the NIS data with the results from density functional theory (DFT), the Fe-N stretching vibrations of both LS and HS phases could be unambiguously identified and the f _LM could be factorized for both phases into a lattice and a molecular part. The structural information from EXAFS and DFT geometry optimization are in reasonable agreement. Received 19 June 2001     

Mössbauer spectroscopic studies of spin crossover in tris(N, N′-dialkyldithiocarbamato) iron (III) complexes: effect of alkyl substituents

Spin crossover behavior in tris(N,N′-dialkyldithiocarbamato) iron(III) complexes with varying alkyl groups has been studied by variable temperature magnetic moment and Mössbauer spectral studies. All the complexes may be divided into three broad groups; high spin (μ _eff > 4.8 BM), intermediate spin (μ _eff?=?3.5???4.6 BM) and low spin (μ _eff?< 3.2 B.M). Room temperature (RT) Mössbauer spectra exhibit an asymmetric doublet resolved into two doublets corresponding to high and low spin states. Estimated % contributions of HS and LS states and calculated μ _eff were comparable with the experimentally determined values. It has been shown that some complexes undergo spin crossover, ⁶A₁g→²T₂g whereas others exhibit spin transitions ⁶A₁g →⁴T₁g or ⁴T₁g → ²T₂g. IR spectra show characteristic ν _(Fe???S) bands in the region 208–285 (HS) and 311–380 cm^???1 (LS). Nature of alkyl groups affects the spin state.     

Light-induced formation of metastable high-spin states in [Fe(mtz)6](CiO4)2

[Fe(mtz)₆](CiO₄)₂ (mtz=1-methyltetrazole) is a spin crossover compound with two different iron(II) lattice sites. Only one of them (lattice site A) shows thermally induced high spin (HS) low spin (LS) spin transition. The LIESST effect (Light-Induced Excited Spin State Trapping) can be observed below 50 K. Complex molecules in B-sites remain in HS state at all temperatures. At 20 K irradiation with red light causes a partial conversion to another HS species, HS(C), with also practically infinite lifetime.In partial fulfilment of the Ph.D. thesis.     

New Hofmann-like spin crossover compound with 3,5-lutidine

A new type III of 3,5-lutidine spin crossover coordination compound with formula Fe(3,5-lutidine)₂Ni(CN)₄·2[(H₂O)(3,5-lutidine)] 2c has been obtained. The ratio of the high spin state (HS) iron (II) changing to the low spin state (LS) iron (II) in 2c is higher than that of type I and type II 3,5-lutidine coordination polymer 2a and 2b previously reported. ⁵⁷Fe Mössbauer spectra of 2c show two different doublets which correspond to HS1 (inner doublet lines) and HS2 (outer doublet lines). The intensity of the HS1 doublet decreases on cooling to 80 K while the intensity of another component, the LS singlet, increases. The 90 % of the HS1 doublet change to the LS singlet is probably due to suitable environments of octahedral iron (II) ions coordinated by four nitrogen atoms of cyano groups and two nitrogen atoms of 3,5-lutidine ligands. We also prepared the Hofmann-like 3,5-dichloropyridine coordination compound Fe(3,5-dichloropyridine)₂Ni(CN)₄ ·2[(3,5-dichloropyridine)(H₂O)] 2d to compare it with 2c. ⁵⁷Fe Mössbauer spectra of 2d show that 2d is not a spin crossover coordination compound.     

Mössbauer spectroscopic study on spin crossover coordination polymer Fe(3-Clpy)2[Pd(CN)4]

⁵⁷Fe Mössbauer spectroscopic results on the alternatively prepared spin crossover coordination polymer Fe(3-Clpy)₂Pd(CN)₄ sample I agree with those of SQUID data. Mössbauer specrum at RT shows two diffrent doublets which correspond to the HS1(inner doublet) and HS2(outer doublet). The intensity of the HS1 doublet decreases on cooling to 78 K at the expense of a new one featuring the LS singlet. Almost 100 % of HS1 change to LS singlet due to iron(II) ions coordinated by four N atoms of cyano groups and two N atoms of 3-Clpy ligand in the sample I. The SQUID data of the sample I prepared by a new direct contact method are different from those of the already reported Fe(3-Clpy)₂Pd(CN)₄ sample. The differences of the SQUID data are associated with particle size effects in molecule spin crossover samples.     

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 Mössbauer 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.     

Spin crossovers in Mott–Hubbard insulators at high pressures

The high-pressure induced phase transitions initiated by electronic transition in 3d ions from the high-spin (HS) to the low-spin (LS) state (HS-LS spin-crossover) are considered. Behavior of the system with d⁶ electronic configuration is investigated in the ground state of zero temperature and critical pressure P_c. Magnetic properties of the Mott–Hubbard insulator (Mg_1−xFe_x)O are studied in the vicinity of the quantum critical point (T=0, P_c). At the critical pressure of spin crossover P_c, the spin gap energy ε_S between HS and LS states is zero. The quantum spins fluctuations HS⇔LS do not require any energy, and the antiferromagnetism is destroyed in the quantum critical point by the first order transition.     

Mössbauer studies of mixed-valence spin-crossover iron complexes with a hexadentate tripod ligand

The spin-crossover behaviors of mixed-valence iron compounds [Fe^IIH₃L][Fe^IIIL](NO₃)₂ (1) and [Fe^IIH₃L^Me][Fe^IIIL^Me](NO₃)₂ (2) have been investigated by ⁵⁷Fe Mössbauer spectroscopy, where H₃L is a hexadentate N₆ tripod ligand containing three imidazole groups and H₃L^Me is its 2-methylimidazole derivative. Deconvolution analyses of the Mössbauer spectra revealed that a two-step SCO (LS Fe^II–LS Fe^III→HS Fe^II–LS Fe^III→HS Fe^II–HS Fe^III) proceeds in each compound on elevating the temperature. Compound 2 exhibited lower spin-transition temperatures than 1. “Frozen-in effect” was observed below 120 and 50 K for 1 and 2, respectively.     

Relevance of Fe atomic volumes for the magnetic properties of Fe-rich metallic glasses

The atomic volume V_a-Fe that can be assigned to Fe atoms in Fe–metalloid (Fe–MD) and Fe–early transition metal (Fe–TE) glasses was deduced in a previous paper (I. Bakonyi, Acta Materialia 53 (2005) 2509) from an analysis of available density data for such amorphous alloys. In the present paper, based on a similarity of the amorphous and face-centered cubic (fcc) structures, the distinctly different magnetic behaviors of these two families of amorphous alloys are discussed in terms of the relative position of V_a-Fe and the critical volume V_fcc?-Fe≈11.7 Å³/atom separating the so-called low-spin (LS) and high-spin (HS) state of fcc-Fe. For Fe–MD systems, V_a-Fe is found to be definitely larger than V_fcc*-Fe whereas for Fe-TE systems V_a-Fe is fairly close to V_fcc*-Fe. Since in topologically disordered alloys a distribution of atomic volumes is inherently present, in Fe–MD glasses the Fe atoms can be assumed to exhibit exclusively the HS state whereas in Fe–TE amorphous alloys a comparable fraction of Fe atoms can be either in the LS or the HS state. According to previous theoretical band structure calculations, an antiferromagnetic state can also be stable just around V_fcc*-Fe. The simultaneous presence of Fe atoms with such a rich variety of magnetic states due to the specific position of the average of the atomic volume distribution can well explain the complex magnetic behavior observed in Fe-rich Fe–TE metallic glasses such as, e.g., in amorphous Fe–Zr alloys around 90 at% Fe.     

Ordering effect on the mechanical,electronic and magnetic properties of the β-based non-canonical approximant phases: β-Al50Cu33Fe17, η-Al50Cu44Fe6 and φ-Al47.5Cu49.5Fe3

Abstract

Using transmission electron microscopy and X-ray diffraction, we established that the ordered η1-Al₅₀Cu₄₄Fe₆ and φ-Al_47.5Cu_49.5Fe₃ (Fmm2) alloys with nano-sized domain structure are formed by slowly cooling, whereas β-solid solutions with a short-range order were found in quenched states. The φ′-modification which exhibits the additional long-period superstructure was also observed in Al_47.5Cu_49.5Fe₃. The studies of low temperature magnetic susceptibility and heat capacity did not reveal any another phase transitions in these alloys. The indentation test showed that hardness and Young’s modulus consistently grow as β-Al₅₀Cu₃₃Fe₁₇ → η1-Al₅₀Cu₄₄Fe₆ → (φ+φ′)-Al_47.5Cu_49.5Fe₃ and approach to those in icosahedral phase. The same trend in the Young’s modulus was obtained for alloys containing β-solid solution with a short-range order. Ab initio calculations, however, predicted the opposite tendency in cubic β-Al₅₀Cu_50?xFe_x with a decrease in x, which was explained by the weakening of the covalent Fe 3d – Al sp bonding. This discrepancy between the results for β- and ordered phases, we related to a crucial effect of ordering which is accompanied by a progressive distortion of cubic local structure in the series β-Al₅₀Cu₃₃Fe₁₇ → η1-Al₅₀Cu₄₄Fe₆ → φ-Al_47.5Cu_49.5Fe_3. As we demonstrated for η-Al(Cu, Fe), these distortions lead to the strengthening of the both covalent Fe–Al and Cu–Al bonds and the higher modules.     

Ab initio cluster calculations of Co3+ spin states in RBaCo2O5.5 (R=Ho, Gd)

Two types of oxygen-deficient perovskites RBaCo₂O_5.5(R=Ho,Gd) related to the “122” type structure (a _p × 2a _p × 2a _p ) have been studied on the basis of ab initio cluster calculations. We consider the peculiar behavior of the trivalent ions Co³⁺(3d ⁶) in either octahedral or pyramidal oxygen coordinations, which is related to a structural first-order phase transition in both compounds. Relative energy positions of low spin (LS, S = 0), intermediate spin (IS, S = 1) and high spin (HS, S = 2) electron configurations are calculated for the low-and high-temperature lattice structures of RBaCo₂O_5.5. A combined analysis of the calculated results and experimental structural data leads to a simple model that captures the most prominent features of the phase transition common to both compounds.     

Spin State of Co<Superscript>3+</Superscript> Ions in Layered GdBaCo<Subscript>2</Subscript>O<Subscript>5.5</Subscript> Cobaltite in the Paramagnetic Phase

A new scheme interpreting the changes in the spin state of Co³⁺ ions in GdBaCo₂O_5.5 in the course of the metal–insulator transition is proposed. The transition occurs gradually within a wide (~100 K) temperature range. The changes in the spin state of Co³⁺ ions are revealed using the data on the linear thermal expansion. In the metallic state, less than one-half of Co³⁺ ions are in the high-spin (HS, S = 2) state in octahedra, whereas the remaining ions are in the low-spin (LS, S = 0) state. The transition to the nonmetallic state occurs owing to the transformation of the HS state to the LS state in octahedra and to the transformation of some part of LS Со3+ in pyramids to the intermediate-spin (IS, S = 1) state.     

Trapping of metastable high-spin species and weak cooperativity in a mononuclear Fe(II) spin-crossover system

The magnetic and structural properties of three gradual spin transition monomeric compounds based on the cation [Fe(Hpt)₃]²⁺ (Hpt=3-(pyrid-2-yl)-1,2,4-triazole) are presented. The non-cooperative character of the spin-crossover in [Fe(Hpt)₃](BF₄)₂·2H₂O (I) is evaluated in light of its calorimetric properties, which yielded the thermodynamic values Δ_trsH=5.81 kJ mol⁻¹ and Δ_trsS=39.5 J mol⁻¹ K⁻¹. The light-induced excited spin-state trapping effect is performed on [Fe(Hpt)₃](BF₄)₂·2H₂O (I) and [Fe(Hpt)₃](SO₄)_0.4(BF₄)_1.2·3H₂O (II), and the subsequent HS→LS relaxations are studied. Their merely first-order kinetics are affected by disorder in the structure of both complexes, which appears in the presence of a distribution of activation energies. HS species can also be frozen-in in I by rapid cooling. Continuous irradiation is shown to induce only apparent light-induced thermal hysteresis effect in I and II, stemming from slow kinetics of relaxation with respect to the kinetics of measurement.     

The influence of the lattice on the spin transition in solids. Investigations of the high spin ag low spin transition in mixed crystals of [FexM1−x(2−pic)3]C12·MeOH

The spin transition behaviour in the iron(II) complex [Fe(2−pic)₃]Cl₂·MeOH (2−pic = 2−aminomethylpyridine) is discussed within a previously developed model which describes the High Spin (HS) ag Low Spin (LS) transition on the grounds of the elasticity theory. For this purpose, the relative HS fraction γ as a function of temperature was determined for mixed crystals of [Fe_xM_1-x(2-pic)₃]Cl₂·MeOH (M = Co, Zn, 0 < x ⩽ 1) employing ⁵⁷Fe Mössbauer spectroscopy. In addition, the temperature dependence of the lattice constants of the pure iron compound was derived from X-ray diffraction measurements and the Lamb Mössbauer factors for [Fe(2-pic)₃]Cl₂·Sol (Sol = EtOH, MeOH) were determined at room temperature. It is shown that essential features of the spin transition behaviour of the title system can be explained within the λ model. The quantitative agreement of the predicted elastic interaction energy with the experimental data, however, is not yet satisfactory.     

EPR of the first Fe(III)-containing spin-crossover metallomesogens

The low-spin (LS) to high-spin (HS) transition in two mesogenic Fe(III) complexes with alkyloxysalicyliden-N^′-ethyl-N-ethylendiamine as ligands is studied by electron paramagnetic resonance (EPR). The symmetrization of the crystal field around the Fe(III) ion under first heating of a polycrystalline sample from the room temperature was observed in the spectra of HS complexes. The line narrowing (from 45 to 15 mT) under the crystal-smectic phase transition is explained by the strengthening of the intermolecular exchange interaction, as a result of the structural reorganization of layers in the smectic phase. A feature of both mesogenic spin-transition systemsis an unusual field-induced spin instability which leads to the hysteresis of the HS-LS composition. This instability is detected by EPR and magnetic susceptibility methods. The alignment of systems by magnetic field in the mesophase and a complete or partial orientational order under cooling the mesophase to the glass state are the main reason for this hysteresis. The influence of EPR-silent LS complexes reveals itself in the line broadening of HS compounds’ when the temperature is lowered from 220 K.