A variable temperature EPR study of Mn(2+)-doped NH(4)Cl(0.9)I(0.1) single crystal at 170 GHz: zero-field splitting parameter and its absolute sign

EPR measurements have been carried out on a single crystal of Mn(2+)-doped NH(4)Cl(0.9)I(0.1) at 170-GHz in the temperature range of 312-4.2K. The spectra have been analyzed (i) to estimate the spin-Hamiltonian parameters; (ii) to study the temperature variation of the zero-field splitting (ZFS) parameter; (iii) to confirm the negative absolute sign of the ZFS parameter unequivocally from the temperature-dependent relative intensities of hyperfine sextets at temperatures below 10K; and (iv) to detect the occurrence of a structural phase transition at 4.35K from the change in the structure of the EPR lines with temperature below 10K.     

DSC study of superionic phase transition in (NH4)4H2(SeO4)3 single crystals

DSC and complex impedance studies of the protonic conductor (NH₄)₄H₂(SeO₄)₃, which undergoes a superionic phase transition of first order at T_s = 378 K show that the activation energy of ionic conductivity d(lg σ)/dt and the ordering enthalpy ΔC_p of the crystal are proportional: d(lg σ)/dT = XΔC_p/RT_s + const, as found for MAg₄I₅ crystals undergoing a second-order superionic phase transition. Thus the short-range order environment of the species involved in fast-ion transport plays the main role in the superionic phase transition. This is also supported by the value of the entropy change at T_s, ΔS = 43 J/mole·K. A new metastable phase was found to be induced on heating the (NH₄)₄H₂(SeO₄)₃ crystal above T_s.     

Anti-Stokes laser cooling in Yb(3+)-doped KPb(2) Cl(5) crystal

We report internal laser cooling in Yb(3+) -doped KPb(2)Cl(5) . From the quantum efficiency values measured in the heating and cooling regions by use of the photothermal deflection technique, we have obtained a room-temperature cooling efficiency of 0.2% in a sample doped with ~5x10(19)ions/cm(3) . Excitation spectra obtained under high irradiation fluences show an excess of fluorescence with regard to those obtained at low fluences, which agrees with the prediction of a model based on photon-ion-phonon interaction.     

Low-temperature structural phase transition in a monoclinic KDy(WO4)2 crystal

The low-temperature thermal and magnetic-resonance properties of a monoclinic KDy(WO₄)₂ single crystal are investigated. It is established that a structural phase transition takes place at T _c=6.38 K. The field dependence of the critical temperature is determined for a magnetic field oriented along the crystallographic a and c axes. The initial part of the H-T phase diagram is plotted for H∥a. The prominent features of the structural phase transition are typical of a second-order Jahn-Teller transition, which is not accompanied by any change in the symmetry of the crystal lattice in the low-temperature phase. The behavior of C(T) in a magnetic field shows that the transition goes to an antiferrodistortion phase. An anomalous increase in the relaxation time (by almost an order of magnitude) following a thermal pulse is observed at T>T _c(H), owing to the structural instability of the lattice. A theoretical model is proposed for the structural phase transition in a magnetic field, and the magnetic-field dependence of T _c is investigated for various directions of the field. Fiz. Tverd. Tela (St. Petersburg) 40, 750–758 (April 1998)     

EPR and optical-absorption studies of Cu2+-doped Zn(NH2(CH2)3NHOH)2Ni(CN)4 single crystals

Electron paramagnetic resonance of Cu²⁺-doped catena-trans-bis(N-(2-hydroxyethyl)-ethylenediamine) zinc(II)-tetra-μ-cyanonicelate(II) [Zn(NH₂(CH₂)₃NHOH)₂Ni(CN)₄] single crystals and powder are examined at room temperature. The spectra show the substitution of the Zn²⁺ ion with the Cu²⁺ ion. The crystal field around the Cu²⁺ ion is nearly axial. There is a single paramagnetic site withg _xx=2.073,g _yy=2.060,g _zz=2.248,A _xx=40.5 G,A _yy=50.8 G,A _zz=172.0 G. The ground-state wave function is an admixture of d _x ²−y ² and d _z ² states. The optical-absorption studies show two bands at 320 nm (31250 cm⁻¹) and 614 nm (16286 cm⁻¹) which confirm the axial symmetry. The crystal field parameters and the wave function are determined.     

Quantum phase transition in the itinerant antiferromagnet (V0.9Ti0.1)2O3

Quantum-critical behavior of the itinerant electron antiferromagnet (V0.9Ti0.1)2O3 has been studied by single-crystal neutron scattering. By directly observing antiferromagnetic spin fluctuations in the paramagnetic phase, we have shown that the characteristic energy depends on temperature as c1 +c2T3/2, where c1 and c2 are constants. This T3/2 dependence demonstrates that the present strongly correlated d-electron antiferromagnet clearly shows the criticality of the spin-density-wave quantum phase transition in three space dimensions.     

Commensurate-incommensurate magnetic phase transition in magnetoelectric single crystal LiNiPO(4)

Neutron scattering studies of single crystal LiNiPO4 reveal a spontaneous first-order commensurate-incommensurate magnetic phase transition. Short- and long-range incommensurate phases are intermediate between the high temperature paramagnetic and the low temperature antiferromagnetic phases. The modulated structure has a predominant antiferromagnetic component, giving rise to satellite peaks in the vicinity of the fundamental antiferromagnetic Bragg reflection, and a ferromagnetic component, giving rise to peaks at small momentum transfers around the origin at (0,+/-Q,0). The wavelength of the modulated magnetic structure varies continuously with temperature. It is argued that the incommensurate short- and long-range phases are due to spin-dimensionality crossover from a continuous to the discrete Ising state.     

A variable temperature EPR study of Mn-doped NH4Cl0.9I0.1 single crystal at 170 GHz: Zero-field splitting parameter and its absolute sign

EPR measurements have been carried out on a single crystal of Mn(2+)-doped NH(4)Cl(0.9)I(0.1) at 170-GHz in the temperature range of 312-4.2K. The spectra have been analyzed (i) to estimate the spin-Hamiltonian parameters; (ii) to study the temperature variation of the zero-field splitting (ZFS) parameter; (iii) to confirm the negative absolute sign of the ZFS parameter unequivocally from the temperature-dependent relative intensities of hyperfine sextets at temperatures below 10K; and (iv) to detect the occurrence of a structural phase transition at 4.35K from the change in the structure of the EPR lines with temperature below 10K.     

Heat capacity, structural disorder, and the phase transition in cryolite (NH4)3Ti(O2)F5

The heat capacity, T-p phase diagrams, and unit cell parameters of cryolite (NH₄)₃Ti(O₂)F₅ were studied over a wide temperature range. A phase transition was found near 226 K, and its thermodynamic characteristics and their dependence on the crystallization conditions were determined. The coordinates and thermal parameters of atoms in the Fm3m phase were refined. An analysis of the electron density distribution and the transition entropy showed that the mechanism of the structural transition involves, above all, rotation of the Ti(O₂)F₅ octahedra. Possible models of disordering of tetrahedral ammonium groups are considered.     

On the low temperature phase transition in (NH4)2SO4

An ultracryostat and multidecameter were used to determine the temperature dependence of the dielectric constant ?′ and dielectric loss ?″ over a wide range of frequencies of single crystals and polycrystalline samples of (NH₄)₂SO₄ in the region of the low temperature phase transition. A sharp increase was observed in the values of ?′ and ?″ at about ?50°C. In addition, a dielectric dispersion was detected and found to be more pronounced in the high temperature phase. This dispersion was attributed to piezoelectric resonance. The observed sudden increase in the values of the dielectric constant and dielectric loss below ? 50°C was attributed to the ferroelectric nature of the low temperature phase of (NH₄)₂SO₄.A DTA thermogram showed a sharp peak at ? 50°C which indicated that the phase transition is one of first order type. A TMA thermogram showed that this transformation was associated with a rapid increase in the expansion coefficient. Such an increase in the lattice parameter might be attributed to the enhanced rotation of electric dipoles associated with the distorted NH₄⁺ and SO₄^2? ions. The distortion of both the ammonium and sulfate ions in addition to their expected orientational motion are suggested to be responsible for the ferroelectric behaviour of ammonium sulfate below ?50°C.A transition to a metastable hexagonal state at about ?40°C is thought to occur, and this transformation is found to be irreversible.     

1H NMR study of molecular dynamics and phase transition in (NH4)2ZnBr4

The proton second moment (M ₂) and spin-lattice relaxation time (T ₁) have been measured in (NH₄)₂ZnBr₄ in the range 77–300 K. The room-temperature spectrum shows a structure which disappears around 243 K. The signal is strong and narrow even at 77 K. Proton T ₁ shows a maximum at 263 K, caused by spin rotation interaction and decreases with decreasing temperature till 235 K, where it shows a sudden increase. Below 235 K, again it decreases and shows a slope change around 216.5 K (reported T_c ). From 216.5 K, T ₁ decreases continuously without exhibiting any minimum down to 77 K. The narrow line at 77 K, and absence of a T ₁ minimum down to 77 K indicate the possibility of quantum mechanical tunnelling in this system. Motional parameters such as activation energy and pre-exponential factor have been evaluated for the reorientational motion of the NH⁺ ₄ ion.     

Conductivity and dielectric relaxation phenomena in (NH4)2SO4 single crystal

AC impedance measurements have been carried out on (NH₄)₂SO₄ single crystals for the temperatures from 300 to 473 K and frequency range between 100 Hz and 4 MHz. The results reveal two distinct relaxation processes in the sample crystal. One is the dipolar relaxation with a peak at frequency slightly higher than 4 × 10⁶ Hz. The other is the charge carrier relaxation at lower frequencies. The frequency dependence of conductivity is described by the relation σ(ω) = Bωⁿ, and n = 1.32 is obtained at temperatures below 413 K. This value drops to 0.2 and then decreases slightly with increasing temperature. The dipolar response of the (NH₄)₂SO₄ single crystal under an ac field is attributed to the reorientation of dipoles. The contribution of charge carriers is increasing substantially with increasing temperature at temperatures above 413 K. The temperature variation of conductivity relaxation peaks follows the Arrhenius relation. The obtained activation energy for migration of the mobile ions for (NH₄)₂SO₄ single crystal was 1.24 eV in the temperature range between 433 and 468 K in this intrinsic region. It is proposed that the NH₄⁺ in the sample crystal has the contribution to the electrical conduction.     

(139La, 55Mn) NMR and magnetic susceptibility data on microscopic phase separation in La0.9MnO3 single crystal

Magnetic susceptibility of the La_0.9MnO₃ single crystal was measured and its (¹³⁹La, ⁵⁵Mn) NMR spectra were recorded. The data obtained indicate that the areas with an A-type antiferromagnetic order (T _N=140 K) and magnetic moments aligned with the b axis occupy a major part of the sample volume in manganite with a considerable concentration of cationic vacancies; simultaneously, the clusters with a canted magnetic sublattice and ferromagnetic interaction between magnetic moments are formed near the vacancies. Charge distribution in these clusters is materially different from that in the antiferromagnetic areas. Magnetic state and relative concentration of the clusters are discussed.     

Synthesis,TGA and EPR studies of phase transitions in Cu2+ doped (NH4)4ThF8 and (NH4)3ThF7

The paper presents the EPR evidence for the occurrence of phase transitions in (NH₄)₄ThF₈ and (NH₄)₃ThF₇. In both cases the Cu²⁺ probe occupies a NH⁴⁺ site and predominantly experiences a dynamic coordination, either due to dynamic Jahn-Teller effect, or due to fluxional behaviour of surrounding (ThF₈)^4- units in (NH₄)₄ThF₈. It is proposed that the structural phase transition in this compound at 214 K is associated with the transition of the dynamic coordination of Cu^2- into a static one, probably due to freezing of motion of (ThF₈)^4- units below this temperature. In (NH₄)₃ThF₇ the dynamic features of the Cu²⁺ EPR spectrum are absent and characteristics of a local orthorhombic symmetry are seen down to 77 K. However, in the high temperature range a change from orthorhombic to axial symmetry is observed at 524 K, possibly due to a phase transition.     

Structural phase transition in elpasolite-like (NH4)2KWO3F3

A new chemical compound, (NH₄)₂KWO₃F₃, was synthesized. The Rietveld-refined crystal structure was found to be cubic at room temperature and to belong to the elpasolite family (space group ). The heat capacity and unit cell parameters were studied within a broad temperature range. A second-order phase transition was found to occur at 235.4 K and to be well described in terms of phenomenological theory. Hydrostatic pressure broadens the temperature interval of stability of the cubic phase (dT₀/dp = −10.8 K GPa⁻¹). A possible model of structural ordering based on a comparison of the entropy parameters and electron density distribution in oxygen and fluorine atoms is discussed.