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.     

Dielectric dispersion in the incommensurate phases of [N(CH3)4]2CoCl4 and [N(CH3)4]2ZnCl4

The complex dielectric permittivity ?(ω) of [N(CH₃)₄]₂CoCl₄ and [N(CH₃)₄]₂ZnCl₄ along the a-axis was measured between 0.35 MHz and 100 MHz. It has been found that for both substances the relaxation frequencies are about 5 MHz at T_c. The dielectric relaxation of both substances could be described by a polydispersive process β = 0.74 in the vicinity of T_c. However, for the temperature region of (T?T_c) > 0.6 for [N(CH₃)₄]₂CoCl₄ the dielectric absorption seems to be rather monodispersive.     

Mössbauer spectroscopic study of the thermal spin crossover in [Fe(II)(isoxazole)6](ClO4)2

The ⁵⁷Fe Mössbauer spectroscopy of mononuclear [Fe(II)(isoxazole)₆](ClO₄)₂ has been studied to reveal the thermal spin crossover of Fe(II) between low-spin (S=0) and high-spin (S=2) states. Temperature-dependent spin transition curves have been constructed with the least-square fitted data obtained from the Mössbauer spectra measured at various temperatures between 84 and 270 K during a cooling and heating cycle. This compound exhibits an unusual temperature-dependent spin transition behaviour with T_C(↓)=223 and T_C(↑)=213 K occurring in the reverse order in comparison to those observed in SQUID observation and many other spin transition compounds. The compound has three high-spin Fe(II) sites at the highest temperature of study of which two undergo spin transitions. The compound seems to undergo a structural phase transition around the spin transition temperature, which plays a significant role in the spin crossover behaviour as well as the magnetic properties of the compound at temperatures below T_C. The present study reveals an increase in high-spin fraction upon heating in the temperature range below T_C, and an explanation is provided.     

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.     

Magneto-optical measurement on the layer type magnet (CH2)2(ND3)2MnCl4

The linear birefringence (LB) of the antiferromagnet (CH₂)₂(ND₃)₂MnCl₄ has been measured as a function of temperature and in magnetic fields up to 100 kOe. The temperature dependence of the LB points to a pronounced two dimensional magnetic behaviour. No anomaly corresponding to the effect of three dimensional ordering could be detected at T_N. In theffield dependent measurements the spin flop at H_SF = 33.6 ± 1 kOe (T = 4K) could clearly be detected.     

Polarisation remanente dans les varietes de basse temperature de (NH4) 3AlF6 ET (NH4) 3FeF6

Dielectric and thermocurrent measurements have been carried out on (NH₄) ₃AlF₆ and (NH₄) ₃FeF₆ ceramic samples. A maximum of permittivity is observed close to the transition temperature (T_{T(NH4) 3AlF6} = 217K; T_T(NH43FeF6 = 264K. In the low-temperature phase a polarization current of about 10^-9A is obtained and can be reversed when the sign of the polarization field is changed, a property which could correspond to a ferroelectric behavior. However, no pyroelectric current is detected when the temperature decreases from T_T. Another hypothesis, based on a field-induced polarization, has been considered : the depolarization current could be due to charge displacements from potential minima favored by rising temperature. In any way, the low-temperature phase is characterized by a remanent polarization.     

Synthesis and characterization of hexakis(acetonitrile)chromium(III) tetrafluoroborate, [Cr(NCMe)6][BF4]3. A nonaqueous Cr source

Oxidation of [Cr^II(NCMe)₄][BF₄]₂ with thianthrinium tetrafluoroborate forms [Cr^III(NCMe)₆][BF₄]₃ exhibiting two ν_CN absorptions at 2331 and 2301 cm⁻¹, and has been structurally characterized with an average Cr-N distance of 1.999 Å. From the electronic absorption spectra the ligand field splitting, Δ₀, is 20,160 cm⁻¹, which is slightly larger than [Cr^III(OH₂)₆]³⁺ in accord with the divalent chromium analogues. The 298 K ESR has a resonance at g=1.9884, and the magnetic susceptibility has a 300 K moment of 3.85μ_B characteristic of S=3/2 Cr(III). The field dependence of the magnetization can be fit to the Brillouin function also characteristic of S=3/2.     

Optical characterization of fourfold (Td)- and sixfold (Oh)-transition-metal species in MgAl2O4:Co by time-resolved spectroscopy

This work investigates the origin of novel visible photoluminescence (PL) bands observed in the spinel MgAl₂O₄:Co²⁺. Besides the well-known fourfold-coordinated Co²⁺(T_d) PL at 670 nm [N.V. Kuleshov, V.P. Mikhailov, V.G. Scherbitsky, P.V. Prokoshin and K.V. Yumashev, J. Lumin. 55 (1993) 265.], a rich structured PL band at 686 nm was also observed that we associate with uncontrolled impurities of sixfold coordinated Cr³⁺(O_h) by time-resolved spectroscopy and lifetime measurements and their variation with temperature. We also show that the lifetime of the Co²⁺(T_d) emission at 670 nm varies from τ=6.7 μs to 780 ns on passing from T=10 to 290 K. This unexpected behaviour for T_d systems is related to the excited-state crossover (⁴T₁↔²E), making the emission band to transform from a narrow-like emission from ²E at low temperature to a broad structureless band from ⁴T₁ at room temperature.     

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.     

Tunneling spectroscopic study on the superconductivity of (TMTSF)2ClO4 crystals

We observed the energy gap spectra for (TMTSF)₂ClO₄-Al₂O₃-Au junctions at 1.5 K by measuring their tunneling current characteristics. The superconducting gap was estimated to be less than 2 meV (T_c<6 K) which is much smaller than the previously reported value, 8 meV.     

Crystal structure and ferromagnetism of (n-C3H7)4N[CoFe(dto)3] (dto=C2O2S2)

Recently, we have discovered a new type of first order phase transition around 120 K for (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] (dto=C₂O₂S₂), where the charge transfer transition between Fe^II and Fe^III occurs reversibly. In order to elucidate the origin of this peculiar first order phase transition. Detailed information about the crystal structure is indispensable. We have synthesized the single crystal of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃] whose crystal structure is isomorphous to that of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃], and determined its detailed crystal structure. Crystal data: space group P6₃, a=b=10.044(2) Å, c=15.960(6) Å, α=β=90°, γ=120°, Z=2 (C₁₈H₂₈NS₆O₆FeCo). In this complex, we found a ferromagnetic transition at T_c=3.5 K. Moreover, on the basis of the crystal data of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃], we determined the crystal structure of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] by simulation of powder X-ray diffraction results.     

EPR studies on exchange interactions in pairs of Jahn-Teller ions in Cu : Zn(pyO)6(ClO4)2

Semi-dilute 10% ⁶³Cu : Zn(pyO)₆(ClO₄)₂ [pyO = C₅H₅NO, pyridine-N-oxide] has been studied by EPR. Spectra of pairs of Cu(pyO)²⁺₆ ions are observed below the transition from dynamic to static Jahn-Teller distortion. Most of these pairs are antiferrodistortively oriented. They exhibit only the type of exchange which corresponds to the interchain interaction J′ in the pure Cu compound. From the Q-band AB type of spectrum it was found that |J′|/k = 0.041 K. An estimate of the zero- point spin reduction could be derived (～36%).     

Phase transitions in [Ni(NH3)6](NO3)2

Electric permittivity ^* = ′ − i″ of nickel-hexammino nitrate (NHN) has been measured within the range of temperature from 9 to 300 K at a frequency of 8.8 GHz (X-band). It has been found that the phase transitions at T_k1 = 247 K and T_k2 = 90 K are discontinuous structural transitions between centrosymmetric phases, whereas the transition at T_c = 63 K is a continuous phase transition (glass?).     

Decoupling of the order-disorder and displacive contributions to the phase transition in NH4H(ClH2CCOO)2

The effects of hydrostatic pressure and substitution of Rb⁺for the ammonium cations on the ferroelectric phase transition temperature in NH₄H(ClH₂CCOO)₂ have been studied by electric permittivity measurements. The transition temperature (T_c) decreases with increasing pressure up to 800 MPa and the pressure coefficient dT_c/dp=−1.4×10⁻² [K/MPa] has been experimentally determined. The substitution of Rb⁺ for the ammonium cations has been shown to considerably lower the ferroelectric phase transition temperature T_c. In mixed crystals, additional electric permittivity anomaly has been clearly evidenced. The results are discussed assuming a model, which combines polarizability effects, related to the heavy ion units, with the pseudo-spin tunnelling.     

EPR study of a new low-temperature phase transition in Zn(ClO4)2·6H2O

From a temperature variation EPR study of Mn²⁺ doped single crystals of Zn(ClO₄)₂·6H₂O phase transition has been detected at T₂~290 K. The phase relationships in this crystal are as follows. Phase I transforms atT₂~346K to Phase II, which in turn transforms to Phase III at T₂ ~ 290K. The latter exists down to at least 220 K. The space group symmetry of crystal may be the same, i.e. Pmn2₁ both above and below T₂. The water-perchlorate sublattice symmetry below T₂ is found to be lower than the P6₃mc symmetry determined previously by X-ray measurements. The onset of a monoclinic or lower symmetry distortion of the water octahedron around a metal ion which starts just below T₂, is reflected through the observed temperature dependence of the rhombic distortion parameter E. It is felt that during this phase transition a change in the degree of configurational disorder associated with the perchlorate tetrahedra takes place, which in turn modifies the hydrogen bonded interaction in the crystal and consequently results in the onset of temperature dependent displacements of the mean positions of the oxygens of the water molecules.     

Hysteresis effects at a cooperative high-spin (5T2) ⇌ low-spin (1A1) transition in dithiocyanatobis (4, 7-dimethyl-1, 10-phenanthroline) iron (II)

Hysteresis has been observed at the cooperative high-spin (⁵T₂) ? low-spin (¹A₁) transition in Fe (4, 7-(CH₃)₂-phen)₂(NCS)₂ where phen = 1, 10-phenanthroline. The transition is centered on T_c> = 121.7 K for rising and on T_c< = 118.6 K for lowering of temperature. The observations are in only qualitative agreement with the thermodynamic theory of Slichter and Drickamer.     

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.     

Ferroelastic phase transition and anomalous elastic and thermal properties of betaine borate (CH3)3NCH2COO·H3BO3

The temperature and pressure derivatives of the elastic constants of orthorhombic betaine borate, (CH₃)₃NCH₂COO·H₃BO₃, have been determined by measuring temperature and stress induced shifts of resonance frequencies of thick plates at ca. 15 MHz in the range between 140 and 300 K and 0 and 3 kbar. The elastic ‘shear’ resistance c₄₄ exhibits a value as low as 0.0492×10¹⁰Nm^-2at 293 K. With decreasing temperature c₄₄ approaches zero at ca. 142.5 K, indicating an acoustic soft mode behaviour connected with a ferroelastic phase transition. The softening of c₄₄ is described in a good approximation by c₄₄(T)_p=0 =alogT/T₀ with a=0.0663×10¹⁰Nm^-2 and T₀ = 139.5 K. Further, c₄₄ decreases with increasing pressure according to the linear relation c₄₄(p)_{T=293 K} = 0.0492?0.184×10^-4p (p in bar, c₄₄ in 10¹⁰ Nm^-2). All other elastic constants show a quite normal temperature and pressure dependence. At 293 K the transition is induced by a pressure of 2.65 kbar. The transition temperature T_c depends linearly on pressure according to T_c = 142.5+0.0568 p (pinbar, T_cinK). Passing through the transition no discontinuous change of the lattice constants is observed. The three principal coefficients of thermal expansion and the pressure derivatives of the dielectric constants exhibit discontinuities at the transition. The transition is of strongly second order.     

Neutron diffraction study of Ho(Rh0.3Ir0.7)4B4

Using powder neutron diffraction techniques, we have examined the magnetic order of the pseudoternary compound Ho(Rh_0.3Ir_0.7)₄B₄ below the Néel temperature T_N=2.7K. The magnetic structure consists of stacked antiferromagnetic basal plane sheets forming a body centered tetragonal unit cell, with a sublattice magnetization corresponding to 9.6±0.6μ_B per Ho³⁺ion at 1.5 K. Magnetic intensity versus temperature measurements indicate that the transition is second order and reveal no anomalous effects when the compound becomes superconducting at T_c=1.34K.     

Magnetic hyperfine interaction and curie temperatures of amorphous (FexNi1−x)80P14B6

Amorphous magnetic glasses (Fe_xNi_1?x)₈₀P₁₄B₆ (0.1 ? x ? 1) have been studied by Mössbauer spectroscopy. At 4.2 K, well-defined and very similar spectra have been observed for samples with different Fe concentration. This suggests that the Fe hyperfine field distribution is insensitive to the amount of dilutant. The value of the average hyperfine field at 4.2 K increases with Fe concentration. A value of 232 kOe is obtained by extrapolating to zero Fe concentration. The relationship $\text{H}{}_{\mathrm{eff}}\text{(O) = (232 + 33}\text{μ}\text{)}\text{kOe}$, similar to that of crystalline Fe-Ni alloys describes the results. The values of T_c = 60 K, 234 K and 425 K have been determined for samples with x = 0.125, 0.25 and 0.375 respectively. The T_C vs. x relation suggests a critical concentration of x_c ? 0.1, above which ferromagnetism exists. By fitting the measured values of T_C to the results of a coherent potential approximation, exchange interaction temperatures of J_FeFe = 617 K, J_FeNi = 800 K and J_NiNi ? 0 K have been obtained.