Magnetic studies on low-spin K3Mn(CN)6

This work reports measurements on single crystals of K₃Mn(CN)₆, of the magnetic susceptibilities and their anisotropies between 300 and 80K. The crystal field model has been extended to include molecular overlap effects for this highly covalent low-spin compound. The magnetic data explain the occurrence of the hot bands around 18,000 cm^?1 reported earlier[1].     

The influence of K4Fe（CN）6 on the photosensitivity of cubic AgCl microcrystal

The influence of K4Fe(CN)6 at various doping concentrations on the photosensitivity of cubic AgC1 microcrysgals has been investigated by using the microwave absorption and phase-sensitive measurement technique. The time behaviour of free photoelectrons in AgCl microcrystals is analysed by using computer simulation as a function of three parameters of shallow electron trap (SET) including doping concentration, trap depth and capture cross-section (CCS).It is found that the three parameters of SET play different roles on the free photoelectron decay time (FDT). After considering the threshold effects of the three parameters and their collective effects, the trap depth value, the CCS value,and the optimal doping concentration of the SET introduced by the dopant K4Fe(CN)6 in cubic AgCl microcrystals can also be determined, and the best photosensitivity of cubic AgCl can be obtained.     

Redox reactions of K3[Fe(CN)6] during mechanochemically stimulated phase transitions of AlOOH

Thermally induced redox reactions of K₃[Fe(CN)₆] (1) were investigated for a broad temperature range by thermal methods and structure analytical methods (ESR and Mößbauer spectroscopy, X-ray Powder diffraction and XANES). Based on the influence of the mechanically activated and transforming matrices 2 and 3, redox processes can be tuned to form doped Al₂O₃ systems which contain either isolated Fe³⁺ centres or redox active phases and precursors like (Al_1−xFe_x)₂O₃ (4), (Al_3−xFe_x)O₄ (5), Fe₃O₄, Fe₂O₃ and Fe⁰. The phase Fe₃C and the chemically reactive C-species were detected during the reaction of 1. The final composition of the doped products of α-Al₂O₃ is mainly influenced by the chemical nature of the Fe doping component, the applied temperature and time regime, and the composition of the gas phase (N₂, N₂/O₂ or N₂/H₂). From the solid state chemistry point of view it is interesting that the transforming matrix (2 and 3) possesses both oxidative and protective properties and that the incorporation of the Fe species can be performed systematically.     

Spin-glass behavior of the polyvinyl pyrrolidone-protected Prussian blue analog K1.14Mn[Fe(CN)6]0.88 nanocubes

Prussian Blue analog K_1.14Mn[Fe(CN)₆]_0.88 nanocubes were synthesized by using polyvinyl pyrrolidone (PVP) as a protective matrix. The PVP-protected MnFe PBA nanocubes with face centered cubic structure are well dispersed with a narrow size distribution of around 50 nm. A spin-glass behavior (including hysteresis, a peak in the zero-field-cooled magnetization and frequency-dependent AC magnetic susceptibility) is observed in the nanoparticles. A possible origin of this spin-glass freezing is discussed. Spin disorder due to the structural defects may be the reason that causes the spin-glass freezing in the MnFe PBA nanoparticles.     

Optical conductivity and electron interaction in the one-dimensional metal K2Pt (CN)4 Br0.3 · 3H2O

Experimental and theoretical investigations of the optical conductivity of K₂Pt (CN)₄Br_0,3 · 3H₂O single crystals for phonon energies near the plasma edge are reported. The imaginary part of the dielectric function is determined by only two scattering processes: Elastic scattering of holes by the Coulomb potentials of randomly distributed Br-ions and inelastic scattering by excitation of plasmons.     

New quasi-one-dimensional tetracyanidoplatinate,Cs4[Pt(CN)4](CF3SO3)2: Synthesis,structure, and physical characterization

The synthesis and some physical properties of a new quasi-one-dimensional tetracyanidoplatinate, Cs₄[Pt(CN)₄](CF₃SO₃)₂ (CsCP(OTf)) are reported and described in comparison to the well-known K₂[Pt(CN)₄]Br_0.30·3.2H₂O (KCP). Single-crystal X-ray diffraction reveals Pt–Pt spacings to be greater than those of KCP by 5% longitudinal and 38% transverse, but much shorter than comparable spacings in other non-partially oxidized platinates. Anomalies are observed between temperatures 100 K and 200 K: (1) Longitudinal DC conductivity is two orders of magnitude higher and is non-monotonic with temperature, showing a minimum at around 170 K. (2) Nuclear magnetic resonance (NMR) longitudinal relaxation time T₁ is at least three orders of magnitude higher than that of KCP, and is also non-monotonic with temperature, showing a sharp peak at around 120 K. Since X-ray diffraction reveals no structural transition at 120 K, these suggest a possible lattice freezing or stiffening at around 120 K.     

Electronic structure of (Nd, Ce)2(Ba, Nd)2Cu3Oy

The dependence of T_c on oxygen content was determined for (Nd_0.67Ce_0.33)₂(Ba_0.67Nd_0.33)₂Cu_3.01O_y. It was found that superconduction appears in a range of y=9.10−9.16 and that T_c is enhanced remarkably by the increase of oxygen content. In an oxygen content range where superconduction appeared, the Ce valence was nearly +4 and the Cu valence changed from 2.31 to 2.33. The conductivity was measured in a wide temperature range between T_c and 1200 K as a function of oxygen partial pressure. The high-temperature conductivity increased with increasing oxygen content. It was found that both carrier concentration and mobility are increased with oxygen content. The conduction at low temperatures was semiconductor-like, and increased with increasing oxygen content, where the energy gap E_A-E_V between acceptor level and top of filled band approached zero.     

Core electron ionization energies and electronic structure of Ti(NO3)4 and Cu(NO3)2

Gas phase X-ray photoelectron spectra of Ti(NO₃)₄ and Cu(NO₃)₂ are reported and discussed in terms of the molecular charge distributions. No measurable splitting is observed between the 1s ionization energies of the chemically distinct oxygen atoms in either molecule. Ab initio calculations for Cu(NO₃)₂ suggest that this is due in large measure to differential orbital relaxation occurring upon core electron ionization.     

Uniaxial stress measurements on Rb2PbCu(NO2)6 and K2PbCu(NO2)6

EPR measurements on crystals of compressed tetragonal Rb₂PbCu(NO₂)₆ and K₂PbCu(NO₂)₆ subjected to uniaxial stress have been carried out at various temperatures. The results indicate that uniaxial stress can reorient the crystal axes in both compounds and that smaller stresses are required for Rb₂PbCu(NO₂)₆ than for K₂PbCu(NO₂)₆ at comparable temperatures. Larger stresses are required at lower temperatures.     

Spin dynamics in (( BEDO-TTF )6[ M (CN)6](H3O,CH3CN)2 ( M = Fe, Cr) crystals

Layered single crystals of the (BEDO-TTF)₆[M(CN)₆](H₃O,CH₃CN)₂ (M = Fe, Cr) compounds with alternating conducting layers of BEDO-TTF and [M(CN)₆](H₃O,CH₃CN)₂ are studied. The contributions to the magnetic susceptibility from charge carriers in BEDO-TTF layers and from the subsystem of localized magnetic moments of iron (or chromium) transition metal complexes are separated for both compounds under investigation. It is revealed that the crystals with [Fe(CN))₆]³⁻ anions at a temperature of ∼80 K and the crystals with [Cr(CN))₆]³⁻ anions at ∼30 K undergo magnetic transitions which are accompanied by drastic changes in the parameters of the EPR lines associated with the BEDO-TTF layers and the subsystem of localized spins of transition metal complexes. It is established that the presence of the BEDO-TTF layers in the structure affects the magnetic properties of iron and chromium hexacyanide complexes. Original Russian Text ? R.B. Morgunov, E.V. Kurganova, T.G. Prokhorova, E.B. Yagubskiĭ, S.V. Simonov, R.P. Shibaeva, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 4, pp. 657–663.     

Specific heat of K2Pt(CN)4Br0.3 · 3H2O

The anomalous behavior of the specific heat appears around 35 and 65 K. The 65 K-anomaly seems to be related to the ferroelastic softening of c₆₆. At 120 K no anomaly appears not only in the normal sample but also in the dehydrated sample.     

Thermal expansion of the one-dimensional conductor K2Pt(CN)4Br0.3·xH2O and K2Pt(CN)4·xH2O

Measurements of the thermal expansion coefficients of K₂Pt(CN)₄Br_0.3· xH₂O and K₂Pt(CN)₄·xH₂O show a large anisotropy of the a-and c- directions. Their temperature dependence could be described by a simple Grüneisen theory. In the range from 80–330°K no anomaly indicating a Kohn-Peierls transition could be found.     

Studies of thermal decomposition of (NH4)2Fe(SO4)2·6H2O

Thermal decomposition products of the Mohr salt (NH₄)₂Fe(SO₄)₂·6H₂O have been studied and identified using the Mössbauer effect, X-ray diffraction, infrared spectroscopy, and the gravimetric and thermal differential methods. It has been found that the Mohr salt heated for 96 hr. in air at 520K changes to a single substance identified as NH₄Fe(SO₄)₂ with a single Mössbauer line (width 0.30 mm/sec; isomeric shift 0.30 mm/sec). When the Mohr salt is heated for 1 hr. in air at 770 K it changes to Fe₂(SO₄)₃ with a single Mössbauer line (width 0.33 mm/sec; isomeric shift 0.31 mm/sec) strikingly similar to line of NH₄Fe(SO₄)₂.     

Crystal growth,structure, electron paramagnetic resonance and magnetic properties of (NH4)2V3O8

A method to grow single crystals of ammonium vanadate (IV, V) (NH₄)₂V₃O₈ has been devised. The crystal structure is tetragonal P4bm; residual factor is R = 0.030. Cell parameters are $\text{a = 8.891 ± 0.004}\text{A}\text{?}$ and $\text{c = 5.582 + 0.002}\text{A}\text{?}$. The V⁵⁺ atom lies at the center of a triangular pyramide (VO₄ tetrahedron) while the V⁴⁺ atom is on A 4-fold rotation axis at the center of a square-based pyramide VO₅ whose symmetry point group is almost C_4v with the short V = O bond lying along the 4-fold axis parallel to the c edge of the tetragonal cell. Crystals are thin platlets with (001) cleavage planes. The platlets have very often a square or rectangular shape limited by {100} or {110} planes. Each single crystal was not large enough to record a good e.p.r. spectrum, but by sticking on the same quartz plate a score of them it was possible to gather enough crystals so to record correct spectra and by orienting the plate to obtain resonance lines separately for g_∥ = 1.9263 et g_τ = 1.9755. Measurements at 283 K on powder samples gave times for spin-spin relaxation T₂ = 0.4 × 10^?7s and for spin-lattice relaxation T₁ = 1.6 × 10^?7s. The magnetic structure is characterized by an exchange narrowing ω_e = 3 × 10¹⁰rad/s which corresponds to a transition temperature of about 0.5 K. Static susceptibility measurements at high magnetic field show a paramagnetic behaviour with an antiferromagnetic interaction which is interpreted in the magnetic space group P_2c4bm as the interaction between V⁴⁺ ions from consecutive planes parallel to (001).     

Paramagnetic properties of several rare earth compounds with K3Ln2(NO3)9 structure

We present measurements of the paramagnetic susceptibilities of K₃Pr₂(NO₃)₉ and K₃Sm₂(NO₃)₉, cubic materials with rare earth sites having threefold rotational symmetry about (111). The rare earth environment resembles that of the Ln₂Mg₃(NO₃)₁₂·24H₂O materials, and the magnetic susceptibilities show similarities but also interesting differences with Pr₂Mg₃(NO₃)₁₂·24H₂O and Sm₂Mg₃(NO₃)₁₂·24H₂O. Paramagnetic resonance experiments in K₃La₂(NO₃)₉ doped with these and several heavier lanthanides are also described and compared with theory.     

Raman scattering in K2Pt(CN)4Br0.3 · 3H2O

Raman scattering experiments on K₂Pt(CN)₄Br_0.3 · 3H₂O are reported between 5 and 300 K as a function of temperature. A line of A₁ symmetry detected at 44 cm^?1 shows interesting temperature dependent properties. It is concluded from a comparison of the frequency, symmetry, and scattering intensity of this line with theoretical predictions that the excitation concerned represents the amplitude mode of the charge density wave (the line observed in infrared absorption being the phase mode). No Peierls transition is observed, but the results are consistent with a Peierls distortion present at all temperatures. The findings are correlated with inelastic neutron scattering and infrared studies. Finally, the CN stretching modes at 2189 and 2173 cm^?1 and the water mode at 3490 cm^?1 are studied as a function of temperature.     

Lattice softening in K2Pt(CN)4Br0.3·3H2O

The temperature dependences of the elastic constants, c₁₁, c₃₃, c₄₄, and c₆₆, in KCP are described. In the temperature range 10–100 K softening is observed in c₄₄, while c₆₆ decreases almost linearly with decreasing temperature. These results indicate the presence of a new critical region.     

Lattice anharmonicities in K2Pt(CN)4Br0.3 · 3H2O

A difference of about 7 per cent between the velocities of first and zero sound has been observed in K₂Pt(CN)₄Br_0.3 · 3H₂O for longitudinal waves travelling along the direction of the Pt chains. Large temperature and pressure derivatives of the elastic module c₃₃ have been found.     

The structure and helicity of perfluorooctanonitrile, CF3–(CF2)6–CN

New molecular structural data is presented for a cyanide terminated oligomer of polytetrafluoroethene. The target molecule, CF₃–(CF₂)₆–CN, has been seeded within a pulsed supersonic expansion of argon. The result of this action is to cool the species to rotational temperatures below 4 K. Within this state, the pure rotational spectrum of the oligomer has been recorded using two types of Fourier transform microwave spectroscopy. A total of 111 transitions have been identified involving rotational J levels between 6 and 40. Only a- and b-type transitions were observed. The spectrum has been analyzed using a Hamiltonian containing all three rotational constants and one centrifugal distortion constant, D_J. The experimental spectroscopic constants have been used to develop an effective molecular structure by scaling the quantum chemical calculated structure. The data shows that the seven carbon perfluorinated chain for the isolated oligomer twists ≈104°. This compares well to the C₇F₁₃-twist of ≈97° anticipated from the X-ray structure of phase II polytetrafluoroethene.