Photoinduced transition of [Fe(CN)5NO] nitroprusside anions to metastable states and electron localization in the (BEDT-TTF)4K[Fe(CN)5NO]2 molecular metal

The crystals of (BEDT-TTF)₄K[Fe(CN)₅NO]₂, representing a quasi-two-dimensional organic metal with conducting layers of bis(ethylenedithio)tetrathiofulvalene (BEDT-TTF) and nonconducting layers containing pho-tochromic nitroprusside anions [Fe(CN)₅NO]^2?, were studied by the method of electron spin resonance. Illuminated by light with a wavelength of 514.5 nm, the organic metal crystals feature the formation of localized paramagnetic centers in the conducting cation layers of BEDT-TTF. The phenomenon of electron localization in the BEDT-TTF layers is related to the light-induced formation of long-lived metastable states of nitroprusside anions.     

ab initio Studies on Molecular Conductor (BEDSe-TTF)2[Fe(CN)5NO]

In this paper the ab initio study using pseudopotential plane wave method with the local spin density functional approximation is presented for the molecular conductor (BEDSe-TTF)₂[Fe(CN)₅NO]. The mean electronic density distributions are obtained, and we find that the extended π orbital of the selenium does not affect the properties of material as assumed in other papers and the "side-by-side" type S...S interaction is the primary interaction between donors. From band structure calculations we analyze the influence of the NO groups on the electronic structure and magnetic properties of molecule. It is shown that the itinerant electrons important to electronic properties in these types of hybrids are delocalized electrons contributed by NO groups, instead of by the 3d electrons of Fe. Additionally, we have found that the localized magnetic moment is also contributed by the NO groups in this molecular conductor. From total energy calculations the molecular structure with the lowest energy is found due to the interaction between split spins, and the particular positions of the NO groups are obtained.     

Mössbauer studies of photochemical reaction products of Ru(bpy)3 2+ iron cyanide double complexes

The reductive and the oxidative electron-transfer photochemical reaction system of light-irradiated the mix solutions of Ru(bpy)₃ ²⁺ with [Fe(CN)₆]^4–, [Fe(CN)₆]^3–, [Fe(CN)₅NO]^2– and PB (Prussian Blue) have been studied. The double complexes which isolated from the precipitates of the photochemical reaction have been identified by means of Mössbauer spectroscopy. In order to clarify the chemical states of these isolated double complexes, we have (prepared and) studied Mössbauer spectra of the double complexes such as [Ru(bpy)₃]₃[Fe(CN)₆]₂.14H₂O, [Ru(bpy)₃]₂[Fe(CN)₆].10H₂O, [Ru(bpy)₃][Fe(CN)₅NO].4H₂O, and [Ru(bpy)₃][PB]₂.xH₂O.     

Coexistence of Magnetism and Conductivity in Bis(ethylenediseleno) Tetrathiafulvalene (BEST) with Octahedral Anions Hexacyanoferrate (III)and Nitroprusside

Using an accurate density-function method, we explore the coexistence of the magnetism and conductivity in bis(ethylenediselena)-tetrathiafulvalene (BEST) with the paramagnetic hexacyanoferrate(III) [Fe(CN)₆]^3- or the photochromic nitroprusside anion [Fe(CN)₅NO]^2-. The total and partial densities of states, and the atomic spin magnetic moments are calculated and discussed. It is found that the up- and down-spin total densities of states (DOS) are continuous in the vicinity of the Fermi level, there is overlap between the HOMO and LUMO in the up-spin subbands and the down-spin subbands, which reveals that these types of compounds have conductive properties. From the total and partial densities of states and atomic spin magnetic moments, it is shown that the spin magnetic moments of (BEST)₄[Fe(CN)₆] is mainly assembled at the iron atom and the cyanogen radical, and the spontaneous magnetic moments for (BEST)₂[Fe(CN)₅NO] come from iron atom, cyanogen and nitric oxide radical. To our best knowledge, it is the first theoretical study on the coexistence of the magnetism and conductivity of these compounds.     

Investigation of the metastable state of Na2[Fe(CN)5NO] · 2H2O by optical spectroscopy I. Comparison of the Raman spectra of the ground and metastable state

When excited by the 514.5 nm radiation of an argon ion laser at temperatures below 150 K crystalline sodium nitroprusside Na₂[Fe(CN)₅NO] · 2H₂O can be transformed into an extremely long-living metastable state. The Raman spectra of the crystal in the metastable state and ground state are compared in the range of 50–2350 cm^-1. In the metastable state the ?(NO)-stretching vibration is shifted by more than 100 cm^-1 to smaller frequencies depending on the orientation of the sample with respect to the crystallographic axis. This indicates the population of the antibonding π¹(NO)-orbital. In addition two new vibrations appear at 566 and 422 cm^-1. The other vibrational frequencies of the molecular ion [Fe(CN)₅NO]^2- are scarcely shifted, but relative intensities change.     

On optical dispersion in transparent molecular systems

The Mössbauer data of the new molecular state of Na₂Fe(CN)₅NO · 2H₂O, generated by coherent light, were investigated, particularly as a function of temperature. Its energetic position is close to the molecular groundstate and separated from the excited electronic states by a wide gap. It is optically generated by an inelastic scattering process. The electric field gradient is solely determined by the asymmetric charge distribution of the valence electrons which have the same symmetry properties as the groundstate. The dynamics of the molecular vibrational oscillators is for the new molecular state identical with that of the groundstate. The thermal conversion of the new states, having infinite radiative lifetime, back to the groundstate is determined at elevated temperatures by a peculiar decay function which solely depends upon the internal thermal agitation of the nitroprusside molecular complex [Fe(CN)₅NO]^2?. There is strong evidence that the new molecular state is not a high-spin state. There is no other state of the molecule known which, in terms of its physical properties, its way of generation and decay, is related to the new state reported.     

Surface sensitivity of low energy electron Mössbauer spectroscopy (LEEMS) using57Fe

Very low energy electrons (LEE) (E _e ≤15 eV) are produced with high intensity directly by Mössbauerabsorption and conversion in the case of⁵⁷Fe [1, 4, 5]. These electrons should be very surface sensitive due to their very low attenuation length compared to the 7.3 keV K-Conversion electrons of⁵⁷Fe [5, 11]. We have examined the surface sensitivity of these resonant LEE, using nonresonant⁵⁶Fe metal and⁵⁶Fe stainless steel foils coated with about 20 Å and 50 Å⁵⁷Fe, respectively. They were exposed to air after evaporation: The 20 Å samples are found to be fully oxidized [5]. Depth Selective Conversion Electron Mössbauer Spectroscopy (DCEMS), performed with a high transmission orange type magnetic spectrometer [5, 6, 13] reveals a two layer structure of the 50 Å samples. Low Energy Electron Mössbauer Spectroscopy (LEEMS) [5] is found to be significantly more surface sensitive than conventional DCEMS, but not as surface sensitive as Auger Electron Mössbauer Spectroscopy (AEMS) using LMM-Auger electrons of 500–600 eV, as expected due to the different mean free path. But because of the very low intensity of these Auger electrons this mode appears to be not very useful for practical application.     

The electronic structure and the ferromagnetic properties of the organic radical 4-methacryloyloxy-2,2,6,6-tetramethyl-1-piperidinyloxyl (MOTMP)

The ab initio method of the full potential linearized augmented-plane-wave has been used to study the electronic band structure and the ferromagnetic (FM) properties of the organic radical MOTMP. The total and the partial density of states and the atomic spin magnetic moments are calculated. The calculation revealed that MOTMP has a stable ferromagnetic ground state and the spin magnetic moment is 1.0 μ_B per molecule, which is in good agreement with the experimental value. It is found that the unpaired electrons in this compound are localized in a molecular orbital constituted primarily of π*(NO) orbital and the main contribution of the spin magnetic moment comes from the NO free radical. It is also found that there exists ferromagnetic intermolecular interaction in the compound.     

Berichtigung

The Fe compounds (Et₄N)₂{[((TSP) (TSPH)Fe]₂suc}³) and K[Fe(TSP) (TSPH)prop] · 3H₂O³) were characterized by means of ⁵⁷Fe Moessbauer spectroscopy and magnetic measurements. In the temperature region from 300 to 390 K the Fe(III) of both compounds undergoes a discontinuous transition from low spin state to high spin state, returning only slowly into low spin state after cooling to room temperature. This process causes a hysteresis behaviour of the magnetic values. The spin crossover is connected with a complex isomerization. Moessbauer spectra of the compounds show a significant asymmetry, which can be explained by relaxation effects according to Blume's theory.     

FLAPW-GGA calculations of the influence of Mn, Fe, and Co impurities on the electronic and magnetic properties of layered oxychalcogenides LaCuSO and LaCuSeO

The electronic and magnetic properties of oxychalcogenides LaCuSO and LaCuSeO with a layered ZrCuSiAs-type structure doped with impurity atoms M = Mn, Fe, and Co have been predicted using the first-principles FLAPW-GGA method. It has been shown that a partial substitution of 3d ^{n < 9} metal atoms for copper atoms in the structure of the initial matrix leads to the transition of the oxychalcogenides (nonmagnetic semiconductors) to the state of a magnetic half-metal with 100% spin polarization of near-Fermi electrons. In this case, the magnetic and conducting properties of the LaCu_{1 ? x} M _x S(Se)O systems are determined by the states of the [Cu₂(S,Se)₂] blocks with magnetic impurities separated by nonmagnetic semiconducting [La₂O₂] blocks.     

Calculation of short range magnetic order in iron

A spin fluctuation theory for itinerant electrons that includes short-range magnetic order (SRMO) is used to calculate the Curie-temperature (T_c and the temperature dependence of the magnetization and the susceptibility of bulk Fe. When spin correlations are included the Curie-temperature is reduced by 9% to T_c = 2000 K. The calculated temperature-dependence of the magnetization and the magnetic susceptibility are in excellent agreement with experimental results.     

Observation of a high spin polarization of secondary electrons from single crystal Fe and Co

The spin polarization of secondary electrons with nearly zero kinetic energy from Fe (100) and Co (10$\text{1}$0), excited with photons of energy between 20 and 60 eV, was found to be 45%±5% for Fe and 35%±5% for Co. This value is higher than the average valence band spin polarization P_b=n_b/n=2.2/8=27% and 1.7/9=19% for Fe and Co, respectively. With increasing kinetic energy, the spin polarization of the secondaries decreases to the value of P_b within the first 5 eV, remaining constant (within statistical error) at higher kinetic energies. As a spin dependent scattering process we propose excitations within the d-bands, which can be shown to be asymmetric with respect to the electron spin. The high net spin polarization of the slowest emitted electrons is obtained by filtering out monitory-spin electrons at the vacuum barrier.     

Laser induced breakdown spectroscopy surface analysis correlated with the process of nanoparticle production by laser ablation in liquids

Linkage isomerism is the coexistence of iso-compositional molecules or solids differing by connectivity of the metal to a ligand. In a crystalline solid state, the rotation is possible for asymmetric ligands, e.g., for cyanide ligand. Here we report on our observation of a phase transition in anhydrous RbMn[Fe(CN)₆] (nearly stoichiometric) and on the effect of linkage isomerism ensuing our interpretation of the results of Mössbauer study in which we observe the iron spin state crossover among two phases involved into this transition. The anhydrous RbMn[Fe(CN)₆] can be prepared via prolonged thermal treatment (1 week at at 80 °C) of the as-synthesized hydrated RbMn[Fe(CN)₆]·H₂O. The latter compound famous for its charge-transfer phase transition is a precursor in our case. As the temperature is raising above 80 °C (remaining below 100 °C) we observe RbMn[Fe(CN)₆] that inherited its F-43 m symmetry from RbMn[Fe(CN)₆]·H₂O transforming to a phase of the Fm-3 m symmetry. In the latter, more than half of Fe^3?+? ions are in high-spin state. We suggest a plausible way to explain the spin-crossover that is to allow the linkage isomerism by rotation of the cyanide ligands.     

Effect of surface chemisorption on the spin reorientation transition in magnetic ultrathin Fe film on Ag(0 0 1)

We have investigated the effect of surface chemisorption on the spin reorientation transitions in magnetic ultrathin Fe films on Ag(0 0 1) by means of the polar and longitudinal magneto-optical Kerr effect (MOKE) and X-ray magnetic circular dichroism (XMCD) measurements. It is found by the MOKE that adsorption of O₂ and NO induces the shift of the critical thickness for the transitions to a thinner side, together with the suppression of the remanent magnetization and the coercive field of the Fe film. This implies destabilization of the perpendicular magnetic anisotropy. On the other hand, H₂ adsorption is found not to change the magnetic anisotropy, though the enhancement of the coercive field is observed. The XMCD reveals that although both the spin and orbital magnetic moments along the surface normal are noticeably reduced upon O₂ and NO adsorption, the reduction of the orbital magnetic moments are more significant. This indicates that the destabilization of the perpendicular magnetic anisotropy upon chemisorption of O₂ and NO originates from the change of the spin-orbit interaction at the surface.     

Spin solitons in molecular magnetic materials with the chiral structure

Quasiperiodic sequences of the maxima of microwave absorption with decreasing amplitudes have been observed in a temperature range of 4–50 K in the electron spin resonance spectra of ferrimagnetic chiral single crystals [Mn{(R/S)-pn}]₂[Mn{(R/S)-pn}₂(H₂O)][Cr(CN)₆]₂, as well as [Cr(CN)₆][Mn(S)-pnH-(H₂O)]H₂O. Theoretical estimates and previous experimental data indicate that the Dzyaloshinskii-Moriya interaction is the main factor determining the chirality of the spin density and the existence of soliton solutions for the spin dynamics in these crystals. The experimental dependences obtained for the distances between the microwave power absorption maxima on the constant component of the magnetic field of the spectrometer correspond to the theoretical predictions for spin solitons in three-dimensional magnetic materials and exhibit another behavior in crystals with quasi-two-dimensional magnetic ordering.     

Magnetic properties of a quasi-one-dimensional organic ferromagnet

A quasi-one-dimensional alternating-spin Heisenberg model is used to describe the charge-transfer organic ferromagnet, which is studied by the Green's function method. The magnetic properties of the charge-transfer organic ferromagnet in different temperature regions are obtained. A formula for the critical temperature T_c is obtained and is found to be related to the spin of donors, to the intrachain exchange interaction, and to the spatial anisotropy parameter. This conclusion can explain T_c of the organic ferromagnet. The spatial anisotropy parameter of the organic ferromagnet [FeCp₂¹][TCNE] we obtained is consistent with the estimated value of Narayan et al. The Curie-Weiss temperature Θ for the organic ferromagnet [CrCp₂¹][TCNE] we obtained is Θ = 15.6 K which is near the experimental result of θ = 22±1 K.     

Low temperature susceptibility of Al- and Fe-Vanadium oxide bronze (VOB): Comparison of AC/DC measurements with calculation

We have measured the ac- and dc-susceptibilities of semiconducting Vanadium Oxide Bronze (VOB) containing Al and Fe donor atoms. Due to structural reasons, the donor atoms are randomly distributed and transfer their three electrons to the non-magnetic vanadium atoms, thereby creating randomly three V⁴⁺ atoms. The magnetic ordering of the vanadium subsystem has previously been attributed to antiferromagnetically coupled spin pairs of V⁴⁺ ions [1]. The measured susceptibilities are similar to those of spin glasses. Comparison of the data with the calculated isothermal susceptibility shows that the system is far away from equilibrium below the magnetic ordering temperatureT _M .     

On bistability in molecular systems: Photomagnetic studies of inorganic complexes

Photo‐induced effects have been detected by magnetic measurements, Mössbauer spectroscopy and reflectivity. The LIESST effect has been achieved in the spin‐crossover system [Fe_xCo_1-x(btr)₂(NCS)₂]·H₂O. We investigated the purely photo‐induced magnetism of a Prussian Blue analogue Rb_0.52Co[Fe(CN)₆]_0.84, 2.31 H₂O, involving an optical electron transfer from Fe^II to Co^III. Inherent aspects of photomagnetic experiments are described: bulk and surface effects, magnetic and electronic metastabilities of the photo‐excited state.     

Ab initio study of the electronic structure and the magnetic properties of polymers Co[N(CN)2]2(L) [L=pyrazine dioxide (pzdo) and 2-methyl pyrazine dioxide (mpdo)] with dual μ- and μ3-[N(CN)2] bridges

The first principle within the full potential linearized augmented-plane-wave (FP-LAPW) method was applied to study the compound of Co[N(CN)₂]₂(L) [L=pyrazine dioxide (pzdo) and 2-methyl pyrazine dioxide (mpdo)] with dual μ- and μ₃-[N(CN)₂]⁻ bridges. The density of states, the electronic band structure and the spin magnetic moment are calculated. The calculations reveal that these two compounds have a ferromagnetic (FM) interaction arising from the 1,5-μ- and μ₃-[N(CN)₂]⁻ bridges. The spin magnetic moment mainly comes from the Co ion with little contribution from N, O and C anions.     

Relation between 2p X-ray photoelectron and Kα X-ray emission spectra of manganese and iron oxides

The high resolution Mn and Fe Kα X-ray emission spectra (XES), and Mn and Fe 2p X-ray photoelectron spectra (XPS) for manganese and iron oxides were measured. The spectra were compared with those of [MnO₄]⁻, [Fe(CN)₆]⁴⁻ and [Fe(CN)₆]³⁻ ions. As the electronic structure of the latter compounds do not change with electron hole creation in the core levels, satellite peaks due to charge transfer are not observed in the 2p XPS spectra, and the peak profiles of metal 2p XPS and Kα XES are governed by the exchange splitting between 2p and valence electrons. The metal 2p XPS spectra of the oxides had satellite peaks, but the XES spectra had no satellites. FWHMs of the metal 2p_3/2 main peaks of the compounds being low spin states are smaller than those of metal Kα₁ XES spectra. However, FWHMs of Mn 2p_3/2 of the manganese oxide were nearly equal to those of Mn Kα₁ XES spectra, and those of Fe 2p_3/2 XPS spectra of the iron oxides are greater than those of Fe Kα₁ XES spectra.