Birefringence,X-ray and neutron diffraction measurements on the structural phase transitions of (CH3NH3)2 MnCl4 and (CH3NH3)2FeCl4

We used optical birefringence, X-ray and neutron diffraction methods with single crystals to study the structural phase transitions of the perowskite-type layer structures of (CH₃NH₃)₂MeCl₄ with Me=Mn, Fe. The Mn-compound shows the following structural transitions at 394 K — a continuous order-disorder phase transition from tetragonal symmetry $\text{I4}\text{mmm}$ to orthorhombic space group Abma (Cmca in reference 10); at 257 K — a discontinuous transition to a second tetragonal modification; at 95 K — a discontinuous transition to a monoclinic phase. For the Fe-compound the corresponding transition temperatures are 328 K and 231 K, respectively. A low temperature monoclinic phase could not be observed. The lattice parameters of the different modifications were determined as a function of temperature. The temperature dependent course of the order parameter has been investigated for the order—disorder transition. For both compounds, all the methods used gave the same value for the critical exponent of β = 0.315.     

Specific heat of (C6H11NH3) CuCl3 (CHAC), a system of ferromagnetic chains

The heat capacity of (C₆H₁₁NH₃) CuCl₃ (CHAC) has been measured for 0.45 < T < 60 K. Three-dimensional ordering is observed at T = 2.214 K. The data in the paramagnetic region can be described by a ferromagnetic $\text{S =}\text{1}\text{2}$ Heisenberg linear chain model system with J/k = +45 ± 5K.     

Force constant calculations of NCl3 and PCl3

A method based on the least-squares fitting of the observed vibrational frequencies, centrifugal distortion constants, mean-square amplitudes, and vibration-rotation interaction constants with respect to the harmonic force constants has been employed to determine the harmonic force field of NCl₃ and PCl₃. The results are compared with those obtained by other authors. An improved structure of PCl₃ has also been determined by analysis of the microwave spectrum of the P³⁷Cl₃ and P³⁵Cl₂³⁷Cl isotopic species. Two structures have been obtained with the following values of the parameters

$\text{r}{}_{\mathrm{s}}\text{(PCl)=2.0450±0.0072}\text{A}\text{?}\text{Cl}\text{P}\text{Cl=100°12′±20′}$

$\text{r}{}_{\mathrm{s}}\text{(PCl)=2.0426±0.0005}\text{A}\text{?}\text{Cl}\text{P}\text{Cl=100°6′±1′}$

     

The spin-flop transition in the nearly one-dimensional antiferromagnets RbNiCl3 and CsNiCl3

A spin-flop transition has been observed in the ordered phase of the nearly one-dimensional antiferromagnets RbNiCl₃ and CsNiCl₃$\text{H}{}_{\mathrm{s?:;}}\text{= 19.3 ± 0.5}\text{and}\text{19.2 ± 0.3}\text{kG at}\text{1.65}\text{K}$, respectively). The transition involves flopping of the spins within the linear chains while the inter-chain order (the “triangular configuration”) is preserved. The low values of H_s?:; imply a small anisotropy parameter (D = -0.05 cm^-1).     

Polymorphism in skinnerite,Cu3SbS3

Phase transitions in Cu₃SbS₃ are investigated under temperature variation using X-ray diffraction and nuclear quadrupole resonance. Below 263 K, Cu₃SbS₃ has the same structure as Wittichenite, the low temperature form of Cu₃BiS₃, space group P 2₁2₁2₁. Between 263 and 395 K it is monoclinic, space group P $\text{2}{}_1\text{c}$, and above 395 K it is orthorhombic, space, group Pnma with the high temperature Cu₃BiS₃ structure. At 295 K, Cu₃SbSe₃ has the orthorhombic space group Pnma with unit cell parameters $\text{a}\text{= 7.97}$, $\text{b}\text{= 10.61}$ and $\text{c}\text{= 6.83}\text{A}\text{?}$.     

Characterization of LiFeCl4 and AgFeCl4 ionic conductors

LiFeCl₄ and AgFeCl₄ are obtained by direct reaction between LiCl or AgCl and FeCl₃ at 300°C and 400°C respectively. Both compounds are monoclinic with $\text{a = 7.02 (1)}\text{A}\text{?}$, $\text{b = 6.33 (1)}\text{A}\text{?}$, $\text{c = 12.72 (4)}\text{A}\text{?}$, β = 92° (30') for LiFeCl₄ and $\text{a = 10.60 (5)}\text{A}\text{?}$, $\text{b = 6.30 (5)}\text{A}\text{?}$, $\text{c = 12.34 (10)}\text{A}\text{?}$, β = 106° (1) for AgFeCl₄.LiFeCl₄ is clearly isotypic of LiAlCl₄. Magnetic measurements characterize in both cases Fe³⁺ ions in a high spin tetrahedral situation. LiFeCl₄ becomes antiferromagnetic at low temperature (T_N?10 K). AgFeCl₄ reveals a more complex situation. On contrary to the silver derivative, LiFeCl₄ is a good ionic conductor with activation energy of 0.78 eV in the solid state below 105°C, and a sharp increase in the lithium mobility at this temperature.     

Ni2+ emission in MgO,KMgF3, KZnF3 and MgF2

The emission of Ni²⁺ ions in MgO, KMgF₃, KZnF₃ and MgF₂ crystals has been investigated. The fine structure on the bands at about 20 000 cm^-1 and 13 000 cm^-1 has been studied in detail and from this and the excitation spectra these bands are assigned to ${}^1\text{T}{}_{\mathrm{2g}}\text{→}{}^3\text{A}{}_{\mathrm{2g}}$ and ${}^1\text{T}{}_{\mathrm{2g}}\text{→}{}^3\text{T}{}_{\mathrm{2g}}$ transitions respectively.     

Structure,vibrational study and conductivity of the trihydrated uranyl bis(dihydrogenophosphate): UO2(H2PO4)2·3H2O

The X-ray structure (293 K) of UO₂(H₂PO₄)₂·3H₂O has been refined (R = 0.062): M_r = 518g, space group: P2₁/c (Z = 4); $\text{a = 10.816(1)}\text{A}\text{?}$, $\text{b = 13.896(2)}\text{A}\text{?}$, $\text{c = 7.481(1)}\text{A}\text{?}$, β = 105.65(1)^°, $\text{V = 1082.7(2)}\text{A}\text{?}{}^3$; D_c = 3.17 Mg m^?3. The structure consists of infinite chains along the (101) axis with U atoms bridged by two H₂PO₄ groups. The U atom is surrounded by a pentagonal bipyramid of oxygen atoms, one of them being an equatorial water molecule. The cohesion between the chains is ensured by hydrogen bonds involving the two last water molecules. An assignment of IR and Raman bands with isotopic substitution spectra is proposed. A phase transition at 128 K was made evident by DSC and spectroscopy. The room-temperature phase is characterized by a high disorder of the OH bond orientation while in the low-temperature phase H₂O and POH species appear well oriented. The conductivity seems to occur by proton transfer and protonic-species rotation at the POH-water molecular interface between the chains. ac conductivity has been determined by means of the complex-impedance method ($\text{σ}{}_{\mathrm{<mtext>RT</mtext>}}\text{～ (3?12) × 10}{}^{\mathrm{?5}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$; E ～ 0.20 eV).     

The elastic behaviour of the ternary zincblende structure semiconductor CuGe2P3

A single crystal has been grown of CuGe₂P₃, a ternary semiconductor with a zincblende structure in which the copper and germanium atoms are randomly distributed on the cation sites. The second order elastic constants measured by the ultrasonic pulse echo overlap technique (C₁₁ = 13.66, C₁₂ = 6.17, C₄₄ = 6.66 and bulk modulus B = 8.67 in units of 10¹⁰Nm^?2 at 291 K) are closely similar to those of GaP and conform well to Keyes' correlation for zincblende structure crystals. The hydrostatic pressure derivatives of the second order elastic constants ($\text{?C}{}_{11}\text{?P}\text{= 4.40}$, $\text{?C}{}_{12}\text{?P}\text{= 3.9}$, $\text{?C}{}_{44}\text{?P}\text{= 0.93}$ and $\text{?B}\text{?P}\text{= 4.07}$) and the third order elastic constants (C₁₁₁ = ? 8.45, C₁₁₂ = ? 3.49, C₁₂₃ = ? 1.13, C₁₄₄ = ? 2.82, C₁₅₅ = ? 1.44 and C₄₅₆ = ? 0.69 in units of 10¹¹Nm^?2) also resemble those of GaP: even the anharmonicity of the long wavelength acoustic modes of this ternary semiconductor resembles that of its binary “parent” compound. The positive signs of the hydrostatic pressure derivatives and the negative signs of the third order elastic constants show that the acoustic modes at the long wavelength limit stiffen under pressure, an effect which is quantified here by computation of the mode Grüneisen parameters, which are all positive. The harmonic and anharmonic force constants, obtained in the valence force field model, fit well into the pattern shown by related zincblende structure compounds: the ratio ($\text{β}\text{α}$) for bond bending (β) to stretching (α) force constants is greater than 4:1; the dominating anharmonic force constant is γ: most of the anharmonicity is associated with nearest neighbour atoms. Analysis of the temperature dependence of the elastic constants on the basis of a simple anharmonic model again emphasises the similarity between the elastic behaviour of CuGe₂P₃ and GaP. The thermal expansion of CuGe₂P₃ varies almost linearly with temperature between 291 K and 1000 K, the linear coefficient of thermal expansion α being 8.21 ± 0.02 × 10^?6 °C^?1. The similar lattice parameters and elastic behaviour of CuGe₂P₃ and GaP indicate that semiconducting devices made of epitaxial deposits of CuGe₂P₃ on a GaP substrate should prove to be almost strain-free.     

Electrical transport properties of a quasi-one-dimensional Nb3Te4 single crystal

The electrical resistance of a linear chain metal Nb₃Te₄ were measured from 1.3 to 320 K. The residual resistance ratio $\text{R(300}\text{K}\text{)}\text{R(4.2}\text{K}\text{)}$ is about 3. Nb₃Te₄ shows an anomaly in the resistivity vs temperature at about 80 K, suggesting an occurrence of a charge-density-wave transition. The transverse and longitudinal magnetoresistance at 4.2 K are proportional to the magnetic field in the range of 2–58 kOe. In the superconducting region close to the transition temperature T_c, the critical magnetic field H_c2 is proportional to δT=T_c?T. The angular dependence of H_c2 fits well with the fluxoid model of the Ginzburg-Landau theory. The ratio of the critical fields parallel and perpendicular to the chain direction is 4.8.     

Low binding energy satellites in the 3d X-ray photoelectron spectra of rare earths (R) in RMn2Si2 and RGa2

The 3_d core-level X-ray photoelectron spectra of rare earths (R) in RMn₂Si₂ (R = Pr, Nd, Sm, Gd) and RGa₂ (R = Pr, Nd, Sm) have been recorded. A structure has been detected on the low binding energy side of each of the 3d_{$\text{5}\text{2}$} and 3d_{$\text{3}\text{2}$} photoemission peaks. The structure identified as a shake-down satellite shows no chemical shift. The energy separation of the satellite has been measured with respect to the main 3d_{$\text{5}\text{2}$} peak. The present results have been examined in the light of recent experimental and theoretical reports.     

Relaxation of the 4G92 state of Nd3+ in LaCl3 and Nd3+ in La(Cl99.6Br0.4)3

The decay of the ⁴G_{$\text{9}\text{2}$} state of Nd³⁺ in LaCl₃ and La(Cl_99.6 Br_0.4)₃ was measured after pulsed laser excitation as a function of temperature. The decay rate is shown to depend besides the radiative transition on single-phonon relaxation between the states ⁴G_{$\text{9}\text{2}$} ($\text{μ =}\text{1}\text{2}$) and ⁴G_{$\text{9}\text{2}$} ($\text{μ =}\text{3}\text{2}$) and on multiphonon orbit-lattice relaxation from ⁴G_{$\text{9}\text{2}$} to ²G_{$\text{9}\text{2}$}. Partial substitution of Cl by Br only alters the radiative lifetime.     

Non-universality in Z3 symmetric spin systems

The critical exponent ν of the mass gap is calculated for a one-dimensional, Z₃ symmetric quantum chain. Using the strong coupling expansion and finite-size scaling it is shown that ν varies continuously from $\text{5}\text{6}\text{to}\text{1}$.     

Phase diagrams of CuCl2·2NC5H5 and CsCuCl3

The phase diagrams of two quasi one-dimensional,$\text{S =}\text{1}\text{2}$ quantum systems CuCl₂·2NC₅H₅ and CsCuCl₃, have been determined experimentally for fields between 0 and 90 kOe. The results show an increase of the Néel temperature as a function of the field, in accordance with earlier observations on manganese systems.     

Spontaneous birefringence and order parameter of KMnF3 below the 186°K transition point

The birefringence of KMnF₃ was measured in a temperature range between 130 and 186°K. It is shown that the birefringence is proportional to the square of displacement of F^- ion and fits closely to $\text{(T}{}_{\mathrm{a}}\text{?T)}{}^{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}$ near the transition point, where T_a lies at about 1.5°K above the transition temperature. Values of the order parameter are determined at each temperature.     

Critical field and specific heat of the anisotropic superconductor Nb3S4

We report on the first measurements of the critical field B_c2 and the specific heat of Nb₃S₄, which is a linear structured compound with a superconducting transition temperature of 3.65 K. The angular dependence of B_c2 is well described by the effective-mass model. The ratio of the critical fields parallel and perpendicular to the c-axis gives a value of 4.6. The small value of the specific heat jump at $\text{T}{}_{\mathrm{c}}\text{(}\text{Δc}\text{γT}{}_{\mathrm{c}}\text{= 0.95)}$ can be explained with an anisotropic gap function.     

The crystal structure of SnYb3Rh4Sn12, a new ternary superconducting stannide

The crystal structure of superconducting SnYb₃Rh₄Sn₁₂ has been determined from single-crystal X-ray diffraction data. This compound is cubic, space group Pm3n, $\text{a}{}_{\mathrm{o}}\text{= 9.676}\text{A}\text{?}$ (1) and has two formulae per unit cell. The structure was solved from Patterson and subsequent Fourier synthesis. The least squares refinement was based on 375 independent reflections. The final R and wR factors were 0.015 and 0.014, respectively. The two Sn(1) atoms occupy the 2a (000) positions, the six Yb atoms the 6d ($\text{1}\text{4}$$\text{1}\text{2}$ 0) positions, the eight Rh atoms the 8e ($\text{1}\text{4}$$\text{1}\text{4}$$\text{1}\text{4}$) positions and the twenty-four Sn(2) atoms the 24k (Oyz) positions (y ～ 0.31, z ～ 0.15). The Sn(2) atoms form a tridimensional array of corner-sharing trigonal prisms whose centers are occupied by the rhodium atoms. The Sn(1) and the Yb atoms occupy the icosahedral and cuboctahedral holes of this array, respectively. They form a sublattice which has the arrangement found in the structure of the A15 compounds. The structure of SnYb₃Rh₄Sn₁₂ can be described as containing two interpenetrated structures, namely Yb₃Sn and RhSn₃, or as having an A15 arrangement of clusters of atoms such as (SnSn₁₂) and (YbSn₁₂). These clusters are bound together by face-sharing among them; and by the rhodium atoms. An analogy is drawn between SnYb₃Rh₄Sn₁₂ and the perovskite-like ternary oxides A′A″₃B₄O₁₂.     

Neutron diffraction in a random two-component magnetic system: CsMn0.96Co0.04Cl3.2D2O

Neutron diffraction expriment has been performed on the quasi-one-dimensional antiferromagnet, CsMn_0.96Co_0.04Cl₃.2D₂O, in which two different magnetic ions with competing spin anistropies are randomly distributed. Magnetic scattering data show that the easy spin axis tilts substantially (～ 40° from the easy axis of Mn salt to that of Co salt at 3.8 K) even for such a dilute mixture. The magnetic ordering temperature T_N can be definitely determined owing to the absence of the diffuse Bragg intensity at T_N, to be 4.80 ± 0.02 K. The obtained value of the critical index, β = 0.23 ± 0.02 is found to be considerably smaller in magnitude than both of those found in the Mn and Co salts. Some possible origins for the small β are discussed. The concentration dependence of T_N IS analyzed in terms of the impurity-linked chain model with $\text{|J}{}_{\mathrm{<mtext>MnCo</mtext>}}\text{|}\text{k}\text{= 14.7}\text{K}$.     

Hole mobility in evaporated layers of As2S3.CdI2

The hole drift mobility in As₂S₃.CdI₂ has been determined using Spear's method. The room-temperature value is 10^?4$\text{cm}{}^2\text{Vs}$, the activation energy 0.2 eV. The hole yield appears to be controlled by geminate recombination.     

Magnetic field dependent optical dephasing in LaF3:Er3+

Optical dephasing of the 5388 Å transition between the lowest Kramers doublets of the ⁴S_{$\text{3}\text{2}$} and ⁴I_{$\text{15}\text{2}$} multiplets of Er³⁺:LaF₃ has been studied by photon echo, optical phase switching and optical free induction decay. Er³⁺?¹⁹F hyperfine interactions produce dephasing which is two orders of magnitude faster than in previously studied non-Kramers systems, but at high field changes in the spin dynamics result in microsecond dephasing. For the lower Zeeman component of ⁴S_{$\text{3}\text{2}$}, T₂ (=6μs) is independent of H₀ whereas for the upper component the dephasing is rapid and strongly field dependent. This is quantitatively accounted for by spin lattice relaxation of the upper component of ⁴S_{$\text{3}\text{2}$}. Below 20 kG concentration and temperature dependent dephasing due to electron spin diffusion is observed.