Phase gratings in the visible and near-infrared spectral range realized by metastable electronic states in Na2[Fe(CN)5NO] · 2H2O

Phase and amplitude gratings in the visible and near-infrared spectral range can be written in SodiumNitro-Prusside (SNP), Na₂[Fe(CN)₅NO] · 2H₂O, single crystals by optical excitation of infinitely long-living metastable electronic states, localized in the [Fe(CN)₅NO]^2– anions. Hence, its photorefractive effect does not depend on dopants or defects. The refractive index is modulated by more thann = 1 × 10^–3 in the red (632.8 nm) andn = 5 × 10^–4 in the near-infrared region (1047 nm). The absorption coefficient is modulated by about = 100 m^–1 at 632.8 nm and 40 m^–1 at 1047 nm. The wavelength dependence ofn can be explained by strong absorption bands in the ultraviolet considering Kramers-Kronig dispersive analysis. The time constant of the write-read-erase processes and the diffraction efficiency depend on light intensity, wavelength and polarization of the light with respect to the crystallographic axes. After excitation of the metastable states the indicatrix is modulated only along thea- andb-axis of the orthorhombic system.     

Holographic recording by excitation of metastable electronic states in Na2[Fe(CN)5NO]·2H2O: a new photorefractive effect

Elementary holographic phase gratings can be written in single crystals of Na₂[Fe(CN)₅NO]·2H₂O, sodiumnitroprusside, by excitation of metastable electronic states in the blue–green spectral range. For light polarized parallel to the crystallographic a and b axes of the orthorhombic crystal the light-induced modulation of the refractive index reaches Δn≈2×10^-3 at λ=514.5 nm. Although the largest population of the metastable states is reached for light polarized parallel to the crystallographic c axis, a photorefractive response is not observed. In contrast to electro-optic photorefractive materials the photorefractive effect depends mono-exponentially on the exposure and on the modulation of the incident light interference pattern. Beam-coupling experiments demonstrate that written gratings are in phase with the interference pattern in correspondence with the fact that the excitation of the metastable electronic states is local. The width of the rocking curve shows that the holographic gratings are written completely over the volume of the crystal. Variations of the wavelengths within the excitation range as well as of the crystal thickness do not influence the maximum photorefractive response. Investigations on the grating vector of the written gratings show unambiguously that charge migration is not responsible for the photorefractive effect. Received: 18 November 1998 / Revised version: 26 January 1999 / Published online: 12 April 1999     

A study of the electric hyperfine interaction at57Fe in Na3Fe(CN)6·2H2O using polarized recoilless gamma radiation

Polarimetric Mössbauer measurements have been carried out to determine the electric hyperfine hamiltonian for the 14.4 keV excited state of an⁵⁷Fe nucleus in monoclinic Na₃Fe(CN)₆·2H₂O. The experiments were made with a single crystal sample using polarized gamma rays emitted from a magnetized source. The data were analyzed using a density matrix formalism and taking into account the change in polarization of the radiation inside the absorber of finite thickness. The quadrupole interaction is nonaxial with =0.52(9) and the main principal axis of the electric field gradient lies in the ac-plane.     

Co[Fe(CN)_5NO]·5H_2O的磁性研究

合成了氰根桥联配合物Co[Fe(CN)5NO].5H2O,使用元素分析、热重分析、红外光谱、XRD对配合物进行了表征。红外光谱显示金属离子通过氰根桥联即FeII-CN-NiII传递磁相互作用,是属于桥式氰根配体的CN伸缩振动,而粉末XRD衍射图表明此化合物为面心立方体结构(FCC),空间群为Fm3m(225),晶格常数a=10.2856。通过对该配合物的直流变温磁化率和交流磁化率测定表明金属离子通过氰根传递弱反铁磁作用,根据Curie-Weiss定律,拟合数据获得居里常数C=1.55cm3·K/mol,顺磁居里温度θ=-1.87K。     

Specific heat of Na1−x V2O5 single crystals

Temperature dependences of the specific heat C and the magnetic susceptibility χ of Na_1?x V₂O₅ single crystals (x=0, 0.01, 0.02, 0.03, and 0.04) are studied. In NaV₂O₅, the transition to the spin-gap state (T _c =34 K) is accompanied by a sharp decrease in χ, while C exhibits a λ-shaped anomaly. At low temperatures, the specific heat of NaV₂O₅ is approximated by the sum of phonon ～T ³ and magnon ～exp(?Δ/T) contributions, which makes it possible to estimate the Debye temperature Θ_D=336 K and the gap in the magnetic excitation spectrum Δ=112 K. With the departure from stoichiometry, the anomalies observed in the behavior of χ and C are spread and shifted to lower temperatures. The low-temperature specific heat of nonstoichiometric samples is determined by the sum of phonon and magnon components and the contribution due to the presence of defects. The values of magnetic entropy characterizing the phase transitions in Na_1?x V₂O₅ are calculated.     

EPR studies of Cu2+ ion in CdK2 (SO4)2·6H2O single crystals

The EPR spectra of Cu²⁺ in CdK₂(SO₄)₂·6H₂O crystals have been studied at 77 K and 300 K in three (bc, a¹c and a¹b) planes. The angular variation spectra showed that the Cu²⁺ ion enters the Cd²⁺ site in the lattice. The principal g and A values, covalency parameter (α'²), mixing coefficients (α and β) and Fermi-contact term (K) have been evaluated from the EPR analysis. The ground-state wave function of the Cu²⁺ ion has been constructed using the α'², α and β values, and the signs for the hyperfine coupling constants are also determined. The covalency value indicates the percentage of unpaired spin density present at the metal (Cu²⁺) d orbital. The nature of the distortion present in the lattice is obtained from the values of the mixing coefficients.     

23Na nuclear magnetic resonance investigation of the lattice distortion in α-NaxV2O5

The full temperature dependence of the electric field gradient tensor at the Na sites has been determined by nuclear magnetic resonance (NMR) in the temperature range 8–330 K in α-Na_{x 2}O₅ (x = 0.996). Above the spin-Peierls transition (T _c = 34.7 K), only a single Na site is observed in agreement with the Pmmn space group proposed to describe this compound as the first example of a 1/4-filled ladder system. Below T_c, eight distinct quadrupolar²³Na sites are observed according to the distortion wave vector k_c = (1/2, 1/2, 1/4) previously reported. In addition, the opening of a spin gap is evidenced by a rapid drop of the magnetic hyperfine shift²³K at T_c. The results are discussed in the context of a charge-order-driven spin-Peierls transition.     

Influence of zeolite water on paramagnetic and ferromagnetic resonances in the Co2[Nb(CN)8] · 8H2O molecular magnet

The contributions of Co²⁺ and Nb⁴⁺ ions to the high-frequency dynamic magnetic susceptibility of the Co₂[Nb(CN)₈] · 8H₂O molecular magnet in the paramagnetic state at T > 12 K are separated. It is found that the ferromagnetic ordering, which leads to the reconstruction of the electron paramagnetic resonance spectrum into the ferromagnetic resonance spectrum, occurs at T < 12 K. The influence of zeolite water on the spectra of the paramagnetic and ferromagnetic resonances is found. Dehydration leads to a decrease in the time of the spin relaxation of the ferromagnetic system from 50 ps to 17 ps at T = 4 K and to the variation in the temperature dependences of the widths of the lines and g factors in the electron spin resonance spectra.     

[Cu(en)2][KFe(CN)6]·H2O的磁性分析

合成了氰根桥联配合物[[Cu(en)2][KFe(CN)6].H2O,使用元素分析、红外光谱等对配合物进行了表征。首次通过对该配合物的磁化率测定表明金属离子通过氰根传递弱反铁磁作用,计算求得分子磁体χmT的实验值与理论值。并根据Curie-Weiss定律拟合获得居里常数C=0.42cm3.K.mol-1和顺磁居里温度=-0.54K。     

Electron paramagnetic resonance of Gd3+ in Nd2(SO4)3 · 8H2O single crystal

Electron paramagnetic resonance study has been carried out in Gd3+ doped single crystals of Nd₂(SO₄)₃·8H₂0 at three different temperatures. Two magnetic complexes exhibiting orthorhombic or lower symmetry are found and the results have been fitted to a suitable spin-Hamiltonian. The ten “best fit” parameters are obtained from two computer programs. Zero-field splittings of Gd3+ have been deduced from spin-Hamiltonian parameters and are compared with those observed directly by Bogle and Symmons. Fine forbidden transitions ∥ΔM_s∥ I > 1 are analyzed using numerical solution of the Hamiltonian matrix.     

Magnetic and Mössbauer studies of cyanide-bridged bimetallic assembly [Mn(cyclam)][Fe(CN)6]·3H2O

Cyanide-bridged bimetallic assembly [Mn(cyclam)][Fe(CN)₆]·3H₂O (cyclam=1,4,8,11-tetraazacyclotetradecane) was synthesized from the reaction of trans-[MnCl₂(cyclam)]Cl with K₃Fe(CN)₆. A linear chain structure consisting of alternating [Mn(cyclam)]³⁺ and [Fe(CN)₆]³⁻ units was indicated by the IR and Mössbauer spectra. The variable-temperature magnetization and Mössbauer measurements revealed that this complex exhibited a long-range ordering below 6.8 K. The magnetic behavior of the complex was based on intrachain ferromagnetic and interchain antiferromagnetic interactions.     

Structure and magnetotransport properties of the new quasi-two-dimensional molecular metal β″-(BEDT-TTF)4H3O[Fe(C2O4)3] · C6H4Cl2

The β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G(A^I=NH ₄ ⁺ , H₃O⁺, K⁺, Rb⁺; M^III=Fe, Cr; G = “guest” solvent molecule) family of layered molecular conductors with magnetic metal oxalate anions exhibits a pronounced dependence of the conducting properties on the type of neutral solvent molecules introduced into the complex anion layer. A new organic dichlorobenzene (C₆H₄Cl₂)-containing conductor of this family, namely, β″-(BEDT-TTF)₄H₃O[Fe(C₂O₄)₃] · C₆H₄Cl₂, is synthesized. The structure of the synthesized single crystals studied by X-ray diffraction is characterized by the following parameters: a = 10.421(1) Å, b= 19.991(2) Å, c= 35.441(3) Å, β = 92.87(1)°, V= 7374(1) ų, space groupC2/c, and Z = 4. In the temperature range 0.5&;2-300 K, the conductivity of the crystals is metallic without changing into a superconducting state. The magnetotransport properties of the crystals are examined in magnetic fields up to 17 T at T = 0.5 K. In fields higher than 10 T, Shubnikov-de Haas oscillations are detected, and the Fourier spectrum of these oscillations contains two frequencies with maximum amplitudes of about 80 and 375 T. The experimental results are compared with the related data obtained for other phases of this family. The possible structural mechanisms of the effect of a guest solvent molecule on the transport properties of the β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G crystals are analyzed.     

双金属化合物[Ni(en)2]3[Fe(CN)6]2·2H2O的变温穆斯堡尔谱研究

合成了一维绳梯链状双金属化合物[Ni(en)2]3[Fe(CN)6]2·2H2O,并对其变温穆斯堡尔谱进行了研究,结果表明该分子磁体中铁的电子态为低自旋Fe3 ,而大的四极分裂值(QS)表明此化合物的[Fe(CN)6]3-单元对称结构发生了形变,低温时出现的磁弛豫谱,给出了在该温度点附近出现铁磁耦合相互作用的信息。     

Stability and stabilization of 2H martensite in Cu–Zn–Al single crystals

The stabilization of the 2H martensitic phase in Cu–Zn–Al single crystals with an electron concentration e/a?=?1.53 was investigated. This orthorhombic 2H martensite was first induced from the cubic β phase by the direct β?→?2H or the indirect β?→?18R?→?2H transformations. On loading the 2H martensite, a transition without hysteresis is observed at a stress which was denoted σ_T1. It was found that this stress is associated with a change in the behaviour of the 2H martensite. A high stabilization of the 2H martensite, around 300?K, is only obtained if an ageing is performed at a stress above σ_T1. Additionally, the stresses of the transformation to another martensitic phase, called 18R₂, were found to be constant when the value of σ_T1 is below the retransformation stress. The 2H martensite and its behaviour on ageing were studied by dilatometry, calorimetry, mechanical testing, optical microscopy and transmission electron microscopy (TEM). Models accounting for the stabilization of the 2H martensite on ageing are proposed.     

Zeeman effect on the nuclear quadrupole resonance of 81Br in single crystals of methyl 4-bromobenzoate, 4,4′-dibromodiphenyl-ether and 4,4′-dibromodiphenylsulphide at 77 K

The Zeeman effect on the N.Q.R. of methyl 4-bromobenzoate, 4,4′-dibromodiphenylether, 4,4′-dibromodiphenylsulphide has been studied at 77 K on single crystals, using the ‘geometric method’. The apparatus used in the measurements, which allows one to maintain any temperature between room temperature and 77 K, is described, and the possible significance of the slight variations in the molecular arrangement found in the present measurements and in those performed at room temperature is discussed.     

Ferromagnetic order and spin-glass behavior in multi-metallic compound Ni1.125Co0.375[Fe(CN)6] · 6.8H2O

Multi-metallic Prussian blue compound Ni_1.125Co_0.375[Fe(CN)₆] · 6.8H₂O has been synthesized. The Mössbauer spectroscopy at room temperature and IR spectra study revealed that the metal ions are bonded through cyanide ligand and the presence of low spin Fe^III(S = 1/2) and high spin Fe^III(S = 5/2) ions, as showed in these structure: Fe^III(S = 1/2)-CN-(Co^II/Ni^II)(96%) and Fe^III(S = 5/2)-NC-(Co^II/Ni^II) (4%). The Curie constant of C = 3.00 cm³ K mol⁻¹ and Weiss paramagnetic Curie temperature of θ = 16.43 K were observed in fitting according to Curie–Weiss law. These results indicate that there existed a ferromagnetic exchange interaction in the complexes. The observed value of coercive field (H_c) and remanent magnetization (M_r) at 4 K for the compound are 497 Oe and 1.03 Nβ. The presence of spin-glass behaviours in the compound is ascribed mainly to domain mobility or domain growth under different cooling conditions.     

Hydrogen spin flip satellite lines associated with the PO2−3 radical in a single crystal of Na2HPO3· 5H2O : Calculated and experimental intensities

Intensities of satellite lines have been calculated for PO²⁻₃ in a single crystal of Na₂HPO₃·5H₂O, based on the known crystallographic structure and unpaired spin distribution in the radical. It was assumed that water protons contribute to the satellite intensity. Variation of the satellite intensity was calculated in the bc plane and data were compared with measured intensities at two orientations. At X-band (9 GHz) the experimental intensity is greater than the calculated intensity by a factor of 3 to 4, probably because of overlap with and borrowed intensity from the main line and the inadequacy of the high field approximation. At Q-band (35 GHz) there is good agreement between the calculated and experimental intensities within 10–20 %. It seems that measurements at higher microwave frequency are more reliable than those at lower microwave frequency for the derivation of the electron-proton distances.