Phase transition in (NH4)3FeF6

By use of Mössbauer spectroscopy we have found that the transition from tetragonal to cubic structure in (NH₄)₃FeF₆ takes place at 263 K. The phase transition exhibits a hysteresis of 0.5 K. The experimental data indicate that the tetragonal deformation found at low temperatures diminishes gradually as the transition temperature is approached. The spectra are influenced by electronic relaxation.     

H nuclear magnetic resonance study of the ferroelastic and superionic phase transitions of (NH4)4LiH3(SO4)4 single crystals

We investigated the temperature dependences of the line shape, spin-lattice relaxation time, T₁, and spin-spin relaxation time, T₂, of the ¹H nuclei in (NH₄)₄LiH₃(SO₄)₄ single crystals. On the basis of the data obtained, we were able to distinguish the “ammonium” and “hydrogen-bond” protons in the crystals. For both the ammonium and hydrogen-bond protons in (NH₄)₄LiH₃(SO₄)₄, the curves of T₁ and T₂ versus temperature changed significantly near the ferroelastic and superionic phase transitions at T_C (=232 K) and T_S (=405 K), respectively. In particular, near T_S, the ¹H signal due to the hydrogen-bond protons abruptly narrowed and the T₂ value for these protons abruptly increased, indicating that these protons play an important role in this superionic phase transition. The marked increase in the T₂ of the hydrogen-bond protons above T_S indicates that the breaking of O-H?O bonds and the formation of new H-bonds with HSO₄^- contribute significantly to the high-temperature conductivity of (NH₄)₄LiH₃(SO₄)₄ crystals.     

Magnetic susceptibility studies of (CH2)3(NH3)2FeCl2Br2 and (CH2)6(NH3)2FeCl2Br2

The magnetic susceptibility of the layered compounds (CH₂)₃(NH₃)₂FeCl₂Br₂ and (CH₂)₆(NH₃)₂FeCl₂Br₂ has been measured in the range 80 < T < 300 K. The results follow a Curie-Weiss behavior in the range 120 < T < 300 K but are field dependent for T < 120 K. The results are interpreted in terms of a two-dimensional antiferromagnetic interaction which is canted. A comparison with the corresponding pure chloride compounds is given.     

Ferroelectricity and phase transition from incommensurate phase into commensurate one in (NH4)2ZnCl4

Phase transition has been found in (NH₄)₂ZnCl₄ at T = 266 ± 0.5 K by NQR method. There is a ferroelectric phase below T_c with a space group P2₁cn and with the trebling of the elementary lattice parameter along the axis c. Above the phase transition temperature in the crystal (NH₄)₂ZnCl₄ an incommensurate phase is realized.     

Spectroscopic investigation of [(NH4)xK1−x]2SnCl6 mixed crystals

Polycrystalline samples of the solid solution [(NH₄)_xK_1?x]₂SnCl₆(0?x? 1) have been investigated by DSC, X-ray diffraction and Raman scattering experiments. Substitution of K⁺ by NH⁺₄ depresses the phase transition temperature T₁. For 0? x ?0.05 a linear temperature coefficient $\text{d}\text{T}{}_1\text{dx=?5.16}\text{K/mol}$ % is obtained. The cubic lattice constant roughly obeys Vegard's law, whereas the linewidth of the SnCl₆^2?F_2g internal vibration displays a nonlinear dependence on composition.     

NMR spectral densities and two dimensional diffusion in TiS2(NH3)1.0 and TaS2(NH3)x

NMR measurements of proton spin-lattice relaxation times T₁ and T_1? in the layered intercalation compounds TiS₂(NH₃)_1.0 and TaS₂(NH₃)_x (x = 0.8, 0.9, 1.0) are reported as functions of frequency and temperature (100 K – 300 K). These observations probe the spectral density of magnetic fluctuations due to motions of the intercalated molecules at frequencies accessible to the T₁ (4–90 MHz) and T_1? (1–100 kHz) measurements. Since the average molecular hopping time (τ) can be changed by varying temperature, different regions of the spectral density can be examined. For T > 200 K, both T^?1₁ and T^?1_1? vary logarithmically with frequency, reflecting the two dimensional character of the molecular diffusion. The temperature dependence of T₁ suggests that a more accurate picture of the short time dynamics is required. No dependence of relaxation rate on vacancy concentration is found.     

Magnetic phase diagram of Ni(NO3)2 6NH3

The magnetic phase diagram of Ni(NO₃)₂6NH₃ was determined from the field and temperature dependence of the magnetic susceptibility. The zero temperature exchange and anisotropy fields were determined to be H_E(0) ≈ 26 kOe and H_A(0) ≈ 0.7 kOe respectively.     

Phase transitions and molecular motions in [Zn(NH3)4](BF4)2 studied by nuclear magnetic resonance, infrared and Raman spectroscopy

Middle infrared absorption, Raman scattering and proton magnetic resonance relaxation measurements were performed for [Zn(NH₃)₄](BF₄) in order to establish relationship between the observed phase transitions and reorientational motions of the NH₃ ligands and BF₄⁻ anions. The temperature dependence of spin-lattice relaxation time (T₁(¹H)) and of the full width at half maximum (FWHM) of the bands connected with ρ_r(NH₃), ν₂(BF₄) and ν₄(BF₄) modes in the infrared and in the Raman spectra have shown that in the high temperature phase of [Zn(NH₃)₄](BF₄)₂ all molecular groups perform the following stochastic reorientational motions: fast (τ_R≈10⁻¹² s) 120° flips of NH₃ ligands about three-fold axis, fast isotropic reorientation of BF₄⁻ anions and slow (τ_R≈10⁻⁴ s) isotropic reorientation (“tumbling”) of the whole [Zn(NH₃)₄]²⁺ cation. Mean values of the activation energies for uniaxial reorientation of NH₃ and isotropic reorientation of BF₄⁻ at phases I and II are ca. 3 kJ mol⁻¹ and ca. 5 kJ mol⁻¹, respectively. At phases III and IV the activation energies values for uniaxial reorientation of both NH₃ and of BF₄⁻ equal to ca. 7 kJ mol⁻¹. Nearly the same values of the activation energies, as well as of the reorientational correlation times, at phases III and IV well explain existence of the coupling between reorientational motions of NH₃ and BF₄⁻. Splitting some of the infrared bands at T_C2=117 K suggests reducing of crystal symmetry at this phase transition. Sudden narrowing of the bands connected with ν₂(BF₄), ν₄(BF₄) and ρ_r(NH₃) modes at T_C3=101 K implies slowing down (τ_R?10⁻¹⁰ s) of the fast uniaxial reorientational motions of the BF₄⁻ anions and NH₃ ligands at this phase transition.     

Two-dimensional critical behaviour in antiferrodistortive Al ur6(CIO4)3 and Ga ur6(ClO4)3

Critical behaviour with dimensionality d = 2 has been observed for the 300 K antiferrodistortive phase transition in Al ur₆(ClO₄)₃ and Ga ur₆(ClO₄)₃ by means of the temperature dependence of the ESR parameter D. The systems exhibited d = 2 behaviour in the static critical behaviour for T<T_c?40 K for T>T_c + 40 K. From the ESR data including line width measurements the local order parameter relaxation rate ω₁ has been obtained for various temperatures above T_c, with a lowest value of ω₁ = 150 MHz at T_c + 15 K     

AC electrical properties of the mixed crystal (NH4)3H(SO4)1.42(SeO4)0.58

The frequency dependence of the AC conductivity of (NH₄)₃H(SO₄)_1.42(SeO₄)_0.58 (NHSSe) has been presented in the temperature range (299-393 K). The conductivity data has been analysed in terms of two theoretical models: hopping over a potential barrier model and quantum-tunnelling model. Values of the exponent s, decrease from 1.08 to 0.91 with increasing temperature and the experimental data revel that the hopping model is the rate determining mechanism.     

Electron spin resonance investigation of the structural phase transitions in Alurea6(ClO4)3 and Ga urea6(ClO4)3

Second order structural phase transitions in Alur₆(ClO₄)₃ and Gaur₆(ClO₄)₃ with T_c ～ 300 K are studied by means of ESR on single crystals doped with the analogous Cr(III) compound. The transitions are antiferrodistortive and of the displacive type, the displacements resulting from the condensation of a X₂ mode $\text{(k = (0}\text{1}\text{2}\text{1}\text{2}\text{))}$ of the ClO₄ ions. The ESR parameters have the same temperature dependence as the order parameters and can be described by D and E～φ～. The space group describing the structure changes from S₆² to S₂¹, and the number of domains is multiplied by three. Above 300 K the crystals already consist of two domains, resulting from a ferrodistortive phase transition D_3d⁶ → S₆². The actual transition temperature of the latter phase transition lies at some temperature above the decomposition temperature of the crystals.     

The effect of hydrostatic pressure on the ferroelectric phase transition in [NH2(CH3)2]3[Sb2Cl9]

The effect of hydrostatic pressure on the ferroelectric phase transition temperature in [NH₂(CH₃)₂]₃[Sb₂Cl₉] (DMACA) has been studied by electric permittivity measurements at pressures up to 400 MPa. The pressure-temperature phase diagram is given. The phase transition temperature (T_c) increases with increasing pressure up to 150 MPa, passes through a maximum and then decreases with a further increase of pressure. The unexpected nonlinear decrease in T_c with pressure increasing above 150 MPa suggests that the mechanism of ferroelectric phase transition in DMACA is different from hitherto assumed.     

Calorimetric and x-ray diffraction studies of the (NH4)3WO3F3 and (NH4)3TiOF5 perovskite-like oxyfluorides

The heat capacity and unit cell parameters of the (NH₄)₃WO₃F₃ and (NH₄)₃TiOF₅ perovskite-like oxyfluorides were measured in the temperature interval from 80 to 300 K; the existence of two and one phase transitions in these compounds, respectively, was demonstrated, and their thermodynamic parameters were determined. The effect of a hydrostatic pressure of up to 0.5 GPa on the phase transition temperatures was studied. Triple points and high-pressure phases were found in the T vs. p diagrams. An analysis of entropy changes suggests that all the structural transformations revealed are associated with the ordering of structural blocks. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 5, 2004, pp. 888–894. Original Russian Text Copyright ? 2004 by Flerov, Gorev, Fokina, Bovina, Laptash.     

Chlorine K X-ray absorption-edge structures of CIS-[Pt(NH3)2Cl2], trans-[Pt(NH3)2Cl2], trans-[Pd(NH3)2Cl2] and (NH4)2PdCl4

The K absorption-edge spectra of the ligand chlorine ion in square-planar complex compounds cis- and trans-[Pt(NH₃)₂Cl₂], trans-[Pd(NH₃)₂Cl₂], and (NH₄)₂PdCl₄ are reported and discussed in connection with the chlorine K absorption spectra of K₂PtCl₄ and K₂PdCl₄, reported previously. The observed chemical shift of a white line at the absorption threshold is interpreted in terms of the difference of the ligand-field splitting of electronic states for metal ions. The white line is attributed to the electronic transition from the Cl^? ls level to the lowest unoccupied antibonding molecular orbital (MO), which is specified by a $\text{MO}\text{b}{}_{\mathrm{1g}}\text{(σ}{}^1\text{)}$ in the square-planar complex with D_4h symmetry. The other absorption structures are regarded as continuum “shape resonances” of the outgoing electron trapped by the cage of the surrounding atoms. The effect of geometrical isomerism is found in the chlorine K absorption spectra of cis- and trans-[Pt(NH₃)₂Cl₂].     

Symmetric logarithmic heat capacity anomaly of the layered manganese compound: Mn(NH3)2Ni(CN)42C12H10

The magnetic susceptibility and the heat capacity of a layered manganese compound Mn(NH₃)₂Ni(CN)₄2C₁₂H₁₀ have been measured down to the antiferromagnetic ordered state. A similar symmetric logarithmic singularity in the heat capacity is found for the isomorphic nickel compound Ni(NH₃)₂Ni(CN)₄2C₁₂H₁₀ has been observed at T_N = 0.172 K.     

Brillouin scattering study of phase transitions in LiK0.80(NH4)0.20SO4 mixed crystals

Brillouin spectroscopy was used to study the phase transitions of LiK_0.80(NH₄)_0.20SO₄ mixed crystals in the temperature range 10-300 K. The relevant elastic stiffness coefficients were evaluated at room temperature. The quasi-longitudinal γ₁₆ and the quasi-transverse γ₁₇ mode frequencies were measured in the above temperature range. From their frequency vs. temperature curve, three different phase transitions were determined. Two of the four phases presented by the crystal were found to be ferroelastic. The observed phases are tentatively assigned through a comparison with the phase transitions undergone by LiKSO₄ and LiK_0.96(NH₄)_0.04SO₄ crystals. An anomalous behavior of the Brillouin linewidth near the 260 K phase transition was observed.     

Proton Dynamics in Letovicite, (NH4)3H(SO4)2: A H and N NMR Spectroscopic Study

The improper ferroelastic phase letovicite (NH₄)₃H(SO₄)₂ has been studied by ¹H MAS NMR as well as by static ¹⁴N NMR experiments in the temperature range of 296–425 K. The ¹H MAS NMR resonance from ammonium protons can be well distinguished from that of acidic protons. A third resonance appears just below the phase transition temperature which is due to the acidic protons in the paraelastic phase. The lowering of the second moment M₂ for the ammonium protons takes place in the same temperature range as the formation of domain boundaries, while the signals of the acidic protons suffer a line narrowing in the area of T_c. The static ¹⁴N NMR spectra confirm the temperature of the motional changes of the ammonium tetrahedra. Two-dimensional ¹H NOESY spectra indicate a chemical exchange between ammonium protons and the acidic protons of the paraphase.     

Study of ionic motion in salts of the type (NH4)2MX6 by NMR relaxation

The proton spin-lattice relaxation time in the laboratory frame, T₁, and rotating frame T_1ρ for polycrystalline cubic (NH₄)₂SiF₆, (NH₄)₂SnBr₆ and (NH₄)₂SnCl₆ have been measured over a temperature range 60–500°K. Reorientation of the ammonium ion is generally the dominant relaxation mechanism and T₁ minima are observed in all samples. Activation energies are low in each case, being 2·2 Kcal/mole for the fluosilicate, 1·44 and 1·24 Kcal/mole for the bromo- and chloro-stannate respectively. For the bromostannate a λ-point occurs at 145°K above which the activation energy apparently decreases to 0·26 Kcal/mole. Anion reorientation is detected in the fluosilicate at high temperatures, the correlation time for this motion being obtained from T_1ρ measurements. There is also some evidence to suggest anion reorientation is becoming important in the stannihalides at high temperatures. The proton T_1ρ in the stannibromide is largely determined by the rapid quadrupolar controlled relaxation of the bromine nuclei. Values for the bromine T₁ are deduced and the quadrupolar relaxation mechanism discussed.     

Improved GaSb surfaces using a (NH4)2S/(NH4)2S04 solution

Bulk (1 0 0) n-GaSb surfaces have been treated with a sulphur based solution ((NH₄)₂S/(NH₄)₂SO₄) to which sulphur has been added, not previously reported for the passivation of GaSb surfaces. Au/n-GaSb Schottky barrier diodes (SBDs) fabricated on the treated material show significant improvement compared to that of the similar SBDs on the as-received material as evidenced by the lower ideality factor (n), higher barrier height (?_b) and lower contact resistance obtained. Additionally, the reverse leakage current, although not saturating, has been reduced by almost an order of magnitude at −0.2 V. The sample surfaces were studied by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The native oxide, Sb–O, present on the as-received material is effectively removed on treating with ([(NH₄)₂S/(NH₄)₂SO₄]+S) and (NH₄)₂S. Analysis of the as-received surface by XPS, prior to and after argon sputtering, suggests that the native oxide layer is ≤8.5 nm.     

The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.