Infrared spectra of solid germane

An IR spectroscopic study has shown that GeH₄ molecules are situated on one set of sites of C, symmetry in phase IV. The III–IV transition at 63 K is apparently a second-order phase transition. In phases II and III the molecules are on sites of C_3v. or C₃ symmetry. The II–III phase transition was observed at 67 K. In solid GeD₄, phase transitions were observed at 68.5 and 77 K. In phases II and III the site symmetry is C_I. The II–III phase transition in GeD₄ is apparently second order. There is evidence that the ν₁, vibration of GeD₄ is IR active in the solid state.     

Structural study of ND4I at high pressures and low temperatures

Abstract

Structure, positional, and thermal parameters of ND₄I were studied at high pressures up to 90 kbar and low temperatures down to 10 K using time-of-flight neutron diffraction. The phase transition from a disordered CsCI-type cubic phase ND₄I(II) into a recently discovered high pressure phase ND₄I(V) was observed at P = 80(5) kbar. Surprisingly, the structure of the high pressure phase V was found to bear a strong resemblance to that of the ambient pressure, low-temperature phase III - tetragonal structure with an antiparallel ordering of ammonium ions, space group P4/nmm. The critical value of the deuterium positional parameter corresponding to the II-V transition is close to the one for the phase transition between the disordered and ordered CsCl-type cubic phases II and IV in other ammonium halides.     

Ionic conductivity of Li2NaK(SO4)2

A DSC study of Li₂NaK(SO₄)₂ in the range 300∽925 K has revealed that the compound undergoes phase transitions at 654, 682, 778 and 866 K, before melting congruently at 900 K. The five phase which are observed are designated I, II, III, IV and V with increasing order of temperature. A comparison of the enthalpy of melting with the transition enthalpies suggests that the phases IV and V are plastic phases. The ionic conductivity was measured in the range 584∽895 K by an ac impedance technique. The phase IV showed the smallest activation energy as determined from the temperature dependence of the conductivity (E_a=0.82 eV). The highest conductivity (1.0 Ω⁻¹ cm⁻¹) was observed in phase V at 895 K.     

Phase transition and ferroelastic property studied by using the Cs nuclear magnetic resonance in a CsHSO4 single crystal

The ¹³³Cs spin-lattice relaxation time in a CsHSO₄ single crystal was measured in the temperature range from 300 to 450 K. The changes in the ¹³³Cs spin-lattice relaxation rate near T_c1 (=333 K) and T_c2 (=415 K) correspond to phase transitions in the crystal. The small change in the spin-lattice relaxation time across the phase transition from II to III is due to the fact that during the phase transition, the crystal lattice does not change very much; thus, this transition is a second-order phase transition. The abrupt change of T₁ around T_c2 (II-I phase transition) is due to a structural phase transition from the monoclinic to the tetragonal phase; this transition is a first-order transition. The temperature dependences of the relaxation rates in phases I, II, and III are indicative of a single-phonon process and can be represented by T₁⁻¹=A+BT. In addition, from the stress-strain hysteresis loop and the ¹³³Cs nuclear magnetic resonance, we know that the CsHSO₄ crystal has ferroelastic characteristics in phases II and III.     

Librational modes and the structure of ammonium nitrate in its high temperature phases

We have measured the temperature dependence of the low frequency Raman spectrum of ammonium nitrate in its solid phases IV, II and I and also in its melt. Librational modes are observed in phases IV and II but disappear in both phase I and the melt. Our results indicate that the NO₃ group is almost freely rotating in the solid phase I.     

Phase transitions in 3,5-dichloropyridine

Abstract

Structural phase transitions in 3,5-dichloropyridine crystal have been studied by calorimetry (150–300 K), X-ray diffraction (300 K), ³⁵Cland ¹⁴N nuclear quadrupole resonance (75–300 K) and vibrational spectroscopy (20–300K). Three phases have been shown to exist: phase I, between 338 and 287.5 K, phase 11, between 287.5 and 167.5 K, and phase 111, below 167.5 K. Phase I is characterised by the space group P 2,/m and Z = 2 whereas phases I1 and 111 remain centrosymmetric but double the unit cell. All the phases are ordered and contain crystallo- graphically equivalent molecules. The I ? I1 transition is of first order and probably of the reconstructive type while the II ? III transition is believed to be displacive. Both transitions are monitored by predominantly R′_x and R′_z librational motions.     

Line width transitions in the deuteron magnetic resonance of polycrystalline ND4Cl,ND4Br,and ND4I

The line width of the deuteron magnetic resonance in polycrystalline ND₄Cl, ND₄Br, and ND₄I has been measured from 300°K down to 115°K. Below 200, 172, and 140°K in ND₄Cl, ND₄Br, and ND₄I, respectively, the line rapidly broadens. In addition, the I ? II transition of ND₄I causes a change of line width. The observed line widths agree with those calculated by the present writers from theVan Vleck second moment formula assuming a Gaussian line shape. For this agreement, in the phases II and III of ND₄Cl and in the phase I of ND₄I the deuteron-halogen interactions should be taken into account, whereas in the phases II and III of ND₄Br and ND₄I they should be omitted.     

Ultraviolet reflectivity of NH4Cl and NH4I in ordered and disordered phases

Near-normal incidence reflectivity spectra below 10 eV of NH₄Cl in phases II and IV and of NH₄I in phases II and III are reported. An interpretation is given by comparing these spectra with those of alkali halides. A temperature shift of the first exciton peak of NH₄I due to ordering of the crystal was found as was the case with NH₄Br. The absence of this effect in NH₄Cl strongly implies the relation to the transition II–III and the tetragonal distortion of the lattice.     

The high-pressure phase diagram of ammonia dihydrate

We have investigated the P–T phase diagram of ammonia dihydrate (ADH), ND3·2D₂O, using powder neutron diffraction methods over the range 0–9 GPa, 170–300 K. In addition to the ambient pressure phase, ADH I, we have identified three high-pressure phases, ADH II, III, and IV, each of which has been reproduced in at least three separate experiments. Another, apparently body-centred-cubic, phase of ADH has been observed on a single occasion above 6 GPa at 170 K. The existence of a dehydration boundary has been confirmed where, upon compression or warming, ADH IV decomposes to a high-pressure ice phase (ice VII or VIII) and a high-pressure phase of ammonia monohydrate (AMH V or VI).     

Raman spectroscopic and optical absorption study of the high pressure behaviour and polymorphism in KO2

Abstract

Raman scattering, visible absorption, and optical observation studies have been made on polycrystalline potassium superoxide (KO₂) in a diamond anvil cell as a function of pressure and temperature. Three new phases are observed. With increasing pressure at 298 K, KO₂ transforms from the well known modified CaC₂ structure (Phase II), to two new phases (VII, and VIII). The transformation from III to VII occurs at about 3.2GPa. Phase VII transforms to phase VIII at about 4.4GPa. However, in some samples phase VII does not occur and phase II transforms directly into phase VIII at about 4.2 GPa. These structural transformations are indicated by marked changes in the Raman spectrum. The transitions out of phase II are also marked by a discontinuous red shift in the optical absorption edge. From optical observations we have also determined the pressure and temperature dependence of the transitions from phase II to the high temperature cubic (B1) phase I as well as from the high pressure phases VII and VIII to a new nonbirefringent phase IX. This new phase IX has the cubic B2 (CsCl) structure as is shown by our recent X-ray synchrotron experiments.     

Study of the optically diffused reflectance and thermal-microstructure for the phase transformation of AgNO3

Optical, microstructural, and thermal properties of the investigated silver nitrate samples were characterized by various techniques, such as X-ray analysis, scanning electron microscopy, UV–Vis–NIR absorption and differential scanning calorimetry (DSC). The presence of structural phase transition [orthorhombic structure (phase II) to rhombohedral structure (phase I)] was checked by DSC and X-ray analysis measurements. The thermal energy required for such transformation is found to be 11.6 J/g. The optical band gaps of AgNO₃ are 1.4 and 2.02 eV for phase II and phase I, respectively, at the low-energy region. But at high-energy region, the optical band gaps are 3.41 and 3.43 eV for phase II and phase I, respectively. Characteristic peaks for AgNO₃ corresponding to (2 1 1), (0 0 4) and (3 5 1) for phase II and (0 0 4), (3 1 1) and (0 2 4) for phase I have been observed. The average crystalline size for AgNO₃ samples and the values of dislocation density δ and the strain ε for the planes of two phases II and I are calculated and also the texture coefficient is determined. Such information can considerably aid in understanding the process of phase transformations in AgNO₃.     

Phase transitions and ordering in urea inclusion compounds with n-paraffins

Urea inclusion compounds consist of a pseudo-hexagonal framework of urea with “infinite” channels parallel to c, into which paraffins are embedded. The compound with hexadecane exhibits phase transitions at ≅ 365, ≅ 148 and ≅ 120 K (phases I–IV), which have been investigated by X-ray and neutron scattering. Phase I is hexagonal with a (longitudinal and orientational) random distribution of the included molecules. In phase II, which uniquely occurs in the adduct with C₁₆H₃₄, a doubling of the lattice constant c₀ of the host structure indicates partial longitudinal ordering. This is assigned to the approximately equal length of the hexadecane molecule and 2c_o leading to mutual deformations of both constituents. The transition II→ III is connected with a lateral orientational ordering of the guest molecules in adjacent channels and a simultaneous orthorhombic deformation of the host. Correlated rotational motions of the included molecules around their long axes are deduced from the increasing critical scattering above T_c In phase IV a crystal-like ordering tendency of the paraffins plays the dominant role, while the host breaks into a heavily disordered domain structure. Experimental results indicate a transformation process as no thermal equilibrium was reached during the measurements. The different ordering mechanisms are discussed in terms of interactions between host and guest, guest and guest along each channel, and guest and guest in adjacent channels.     

A Study of the Thermal Hysteresis in AgNO3

The reversible phase transformation of AgNO₃ is studied. Dielectric constant, d.c. resistivity, differential thermal analysis (DTA) and dilatometric measurements show the occurrence of a reversible phase transition II→I at 160°C with heat of transformation H = 0.78 kcal/mol. The thermal hysteresis in this reversible transformation is examined, the magnitude of the temperature hysteresis does not exceed 12°C. An acceptable agreement is observed between the measured values of the transition temperature obtained by three different experimental techniques. The dilatometric analysis shows that this transition is accompanied by thermal shrinkage with relative shrinkage coefficient 8 × 10^?4. Thermal analysis are also used to get thermodynamic and kinetic data of this phase transition. The temperature dependence of the dielectric constant and d.c. resistivity for single crystals as well as polycrystalline samples of AgNO₃ have clearly located and confirm the phase transitions II→I→II with a strong support to its thermal hysteresis character. The conduction mechanism is found to be activated by energy 0.12 eV for phase I and 0.36 eV for phase II. The observed thermal behaviour of the various measured parameters is attributed to orientational disorder of the nitrate group leading to an order-disorder phase transition which is reported here for first time in AgNO₃.     

Phase diagram of Bi up to 140 kbars

The phase diagram of Bi has been studied by resistometric techniques in the temperature range of 30 to 300°K up to pressures of 140 kbars. Using the original Bridgman phase notation, the phase transitions I–II, II–III, I–III, III–IV and V–VI were observed. Two new phases, designated VIII and IX were observed in this region. The triple points occurring between I–II–III near 29.5 kbars and 160°K, between IV–V–VIII near 55 kbars and 240°K, between V–VI–VIII near 72 kbars and 255°K and between VI–VIII–IX near 135 kbars and 250°K. Earlier measurements were adjusted to the 1970 Drickamer pressure scale and compared to the present results. A phase diagram is proposed for pressures to 140 kbars. Calculations of the volume changes and latent heats of transformation are made near the triple points I–II–III, IV–V–VIII and V–VI–VIII using the measured volume changes of Bridgman for the I–II, IV–V and V–VI transitions. The latent heat associated with the III–IV transition was calculated using the volume data of Bridgman to be less than ? 2 cal/mol.     

The Raman spectra of NH4I at high pressures. The existence of a new phase in the ammonium halides

The Raman spectra of NH₄I and ND₄I show significant changes at higher pressures which can only be interpreted in terms of the existence of a new phase. This is not an intermediate phase occurring between phases II and IV, but is observed upon further compression of the ferro-ordered phase IV. Preliminary measurements show that the same phase transition occurs in NH₄Br and NH₄Cl, but at significantly higher pressures than the one in NH₄I.     

Evidence for a spin flop phase in gadolinium arsenate

Thermal resistivity and the magnetization of GdAsO₄ which is antiferromagnetic below 1.62 K are reported. A comparison with GdVO₄ would suggest there ought to be a spin flop phase in which thermal conduction by magnons could be detected. We have observed this spin flop phase.     

Pressure induced phase transformations and band structure of different high pressure phases in tellurium

We report here high-pressure x-ray diffraction (XRD) studies on tellurium (Te) at room temperature up to 40 GPa in the diamond anvil cell (DAC). The XRD measurements clearly indicate a sequence of pressure-induced phase transitions with increasing pressure. The data obtained in the pressure range 1 bar to 40 GPa fit five different crystalline phases out of Te: hexagonal Te (I) → monoclinic Te(II) → orthorhombic Te (III) → Β-Po-type Te(IV) → body-centered-cubic Te(V) at 4, 6.2, 11 and 27 GPa, respectively. The volume changes across these transitions are 10%, 1.5%, 0.3% and 0.5%, respectively. Self consistent electronic band structure calculations both for ambient and high pressure phases have been carried out using the tight binding linear muffin tin orbital (TB-LMTO) method within the atomic-sphere approximation (ASA). Reported here apart from the energy band calculations are the density of states (DOS), Fermi energy (E _f) at various high-pressure phases. Our calculations show that the ambient pressure hexagonal phase has a band gap of 0.42 eV whereas high-pressure phases are found to be metallic. We also found that the pressure induced semiconducting to metallic transition occurs at about 4 GPa which corresponds to the hexagonal phase to monoclinic phase transition. Equation of state and bulk modulus of different high-pressure phases have also been discussed.     

Proton magnetic resonance study of the low-temperature phase transition in a LiNH4SO4 single crystal

The proton NMR line width and spin-lattice relaxation times for LiNH₄SO₄ single crystal were studied at low temperature range of 6 and 280 K. The changes in the proton relaxation behavior near the phase transition temperature indicates a change in the state of internal motion at the transition. The molecular motions obtained by the spin-lattice relaxation processes were found to be determined by molecular reorientation of the NH₄ ions in phases III, IV, and V. We also confirmed that the phase transitions occur at 26 and 133 K.     

High-temperature structural phase transition in the LiCu2O2 multiferroic

The results of thermogravimetric, X-ray diffraction, and electrical studies of LiCu₂O₂ single crystals in the temperature range 300–1100 K are presented. A reversible first-order phase transition between the orthorhombic and tetragonal phases is found to occur in these single crystals at T = 993 K. A pronounced peak on a differential thermal analysis curve and jumps in the unit cell parameters and the electrical resistivity are detected at the phase-transition temperature. The data on the crystal structure of LiCu₂O₂ and the phase transition-induced change in the entropy determined in this work are used to conclude that the revealed phase transition is caused by the ordering-disordering of Li⁺ and Cu²⁺ cations in their structural positions.