The low temperature heat capacity and electrical resistivity of ReO3

Low temperature heat capacity and electrical resistivity measurements are reported for ReO₃. The heat capacity data give an acoustical mode Debye temperature θ = 327 K, and an electrronic density of states parameter γ = 2.83 mJ/mole-K². The observed temperature dependence of the resistivity is consistent with the existence of electron scattering both from acoustic mode phonons and from optical mode phonons of characteristic temperature θ_E = 1080 K. The above measurements are used to evaluate the electron-phonon interaction parameter λ = 0.24.     

Pressure-induced structural phase transition in ReO3

We have investigated the pressure-induced structural phase transition in ReO₃ by neutron diffraction on a single crystal. We collected neutron diffraction intensities from the ambient and high pressure phases at P=7 kbar and refined the crystal structures. We have determined the stability of the high pressure phase as a function temperature down to T=2 K and have constructed the (P-T) phase diagram. The critical pressure is P_c=5.2 kbar at T=300 K and decreases almost linearly with decreasing temperature to become P_c=2.5 kbar at T=50 K. The phase transition is driven by the softening of the M₃ phonon mode. The high pressure phase is formed by the rigid rotation of almost undistorted ReO₆ octahedra and the Re-O-Re angle deviates from 180°. We do not see any evidence for the existence of the tetragonal (P4/mbm) intermediate pressure phase reported earlier.     

Electronically induced lattice distortion in WO3 and stability of ReO3 lattice

Structural phase transitions in WO₃ and the stability of cubic ReO₃ and M_xWO₃ lattices are attributed to the screening effect involving W or Re 5d and O 2p states on the lattice vibrations. The presence of the conduction electrons in ReO₃ or M_xWO₃ is shown to suppress this effect and to stabilize the cubic lattice.     

Dielectric properties and temperature stability of BaTiO3 co-doped La2O3 and Tm2O3

The influence of La₂O₃ and Tm₂O₃ co-doping on the dielectric properties and the temperature stability of BaTiO₃ was investigated. BaTiO₃ ceramics were prepared with the compositional formula of (Ba_1−xLa_x)(Ti_1-x/4−yTm_y)O₃. La₂O₃ and Tm₂O₃ co-doping in BaTiO₃ mainly had effects on an increase in the dielectric constant and the temperature stability, respectively. The increase of La₂O₃ concentration and the decrease of Tm₂O₃ concentration in BaTiO₃ resulted in a decrease of lattice parameter and tetragonality because La³⁺ ion substituting for Ba site is smaller than Ba²⁺ ion and Tm³⁺ ion substituting for Ti site is larger than Ti⁴⁺ ion. With the increase of La₂O₃ and the decrease of Tm₂O₃, the dielectric constant of BaTiO₃ was enhanced in spite of the reduction of tetragonality. P-E hysteresis measurements revealed that this phenomenon was based on the improvement of remanent polarization with the increase of La₂O₃ concentration. The introduction of excess Tm₂O₃ in BaTiO₃ suppressed the grain growth and BaTiO₃ ceramics showed higher temperature stability due to the stable tetragonal structure and the small grain size with the increase of Tm₂O₃ concentration.     

Ultraviolet absorption spectrum of Cr2O3 from reflectivity measurements

Reflectivity measurements have been made on Cr₂O₃ single crystals in the energy range 1.2 eV to 20.0 eV. The results, which include three absorption peaks not previously reported, have been analysed both in terms of the crystal splitting of energy levels of the Cr³⁺ ion and of charge transfer.     

High temperature heat capacity of the LaSn3 and CeSn3 compounds

The high temperature heat capacities of LaSn₃ compound and CeSn₃ intermediate valence compound have been obtained from enthalpic contents measurements, using the technique of drop calorimetry in the 400–1200 K temperature range.The heat capacity behaviour of CeSn₃ has been compared with that of LaSn₃ and the quantitative difference between the two trends is explained in terms of residual promotional energy of the 4? electron of Ce to the conduction band.     

Anomalous ultrasonic velocity of the transverse wave in KH3(SeO3)2

The ultrasonic velocity of the transverse wave with q = [010] and ξ = [001] measured as a function of temperature at 5 MHz in centrosymmetric KH₃(SeO₃)₂ shows a large anomaly with a tendency to approach zero at the transition temperature.     

The heat capacity of LaPd3 and PrPd3 at low temperature

Values of γ=0.33±0.01 mJ/K²·g atom and θ_D=176±1 K were found for LaPd₃. PrPd₃ shows magnetic ordering below 0.6 K and a Schottky anomaly whose maximum lies around 1.8 K. The crystalline field at the Pr³⁺ site creates a Γ₃ (doublet) excited state lying 4 K above the Γ₅ (triplet) ground state.     

Lithium insertion to ReO3-type metastable phase in the Nb2O5–WO3 system

Lithium insertion to distorted ReO₃-type metastable solid solution Nb_xW_1−xO_3−x/2 (0≤x<0.25) has been studied by chemical and electrochemical methods. In the course of lithium insertion into tetragonal compounds, transition to a cubic phase was found to occur in the region where values of y (in Li_yNb_xW_1−xO_3−x/2) fall between 0.2 and 0.3, and the phase transition was found to depend on the conditions of the reaction. Changes in OCV and lattice parameters in tetragonal region (y<0.2) were discussed from the viewpoint of the ordering of lithium ions. Also, the component diffusion coefficient of lithium in tetragonal compounds Li_0.1Nb_xW_1−xO_3−x/2 (0≤x≤0.23) was found to increase with niobium content when x≤0.10, and to saturate at 4×10⁻⁹ cm²/s.     

Low and room temperature measurements and calculations of O2-broadening coefficients in the ν3 band of CS2

O₂-broadening coefficients have been measured for 16 lines in the P and R branches of the fundamental ν₃ band of ¹²C³²S₂ at room and low temperatures (298.0, 273.2, 248.2, 223.2, and 198.2 K), using a tunable diode laser spectrometer and a low temperature cell. These lines from P(62) and R(64) are located in the spectral range 1519-1547 cm⁻¹. The collisional half-widths are obtained by fitting each observed profile with the Voigt and Rautian lineshape models. The broadening coefficients have also been calculated at all experimental temperatures using a semiclassical calculation performed by considering in addition to the electrostatic quadrupole-quadrupole interaction, a simple anisotropic contribution. Finally, from all the results, the parameter n of the temperature dependence of the broadening coefficients has been determined both experimentally and theoretically.     

Low temperature far IR spectra of (CH34)N NiCl3, (CH3)4N NiBr3 and (CD3)4N NiBr3

The known phase transition in (CH₃)₄N NiCl₃, at 171 K, has been characterised by far IR spectroscopy. The transition is explained as due to a formation of weak labile C-H,…, Cl hydrogen bonds at low temperatures, restricting the “free” internal rotations of the methyl groups and perhaps at the same time ordering the orientations of the tetramethylammonium ions. No similar transition in (CH₃)₄N NiBr₃ was found.     

Low temperature heat-capacity measurements of V3Ga and Nb3Al

By low temperature heat capacity measurements using the a.c. technique, we show indirectly that martensitic transformations do occur in V₃Ga and Nb₃Al.     

Electrical transport measurements in TiS3

Results of measurements of conductivity and Hall coefficient in the temperature range 15–300K and of thermal emf in the temperature range 80–400K, carried out on TiS₃ samples, are reported. The results indicate that these crystals are semiconducting with extrinsic n-type conductivity. The mobility of the carriers is about 30 cm²/V sec at room temperature, increases up to about 100 cm²/V sec at 100K and drops at lower temperatures. The Seebeck coefficient is in qualitative agreement with these findings but its detailed temperature dependence is not yet understood.     

Interferometric measurements of thermal expansion coefficients and birefringence of α-LiIO3 with temperature

Variations of the thermal expansion coefficients and birefringence of α-LiIO₃ versus temperature are reported between 20°C and 240°C. The measurements are performed using an interferometric method which is described. No important anomaly appears at the α-γ phase transition.     

Heats of solution/substitution in TlNO3 and CsNO3 crystals and in RbNO3 and CsNO3 crystals from heats of transition: the complete phase diagrams of TlNO3-CsNO3 and RbNO3-CsNO3 systems

From measurements of the decrease in the heat (enthalpy) of transition in the solid phase using differential scanning calorimetry, the apparent molar heats of solution, slope ΔH_t/x, the partial molar heats of solution at infinite dilution, χ, and the heats of solution, ΔH_s^°, of Tl⁺ in CsNO₃ crystal and Cs⁺ in TlNO₃ crystal and Rb⁺ in CsNO₃ crystal and Cs⁺ in RbNO₃ crystal along with their recovered lattice energies, ΔH_L^°, are reported. ΔH_s^° of Tl⁺ and Rb⁺ in CsNO₃ crystal are each found to be negligible or zero representing an ideal solid solution, i.e. ΔH_mix=0. The complete phase diagrams of the TlNO₃-CsNO₃ and RbNO₃-CsNO₃ systems with details of the sub-solidus regions are included. The properties of Tl_(1−x)Cs_xNO₃ and Rb_(1−x)Cs_xNO₃ compositions are discussed in terms of a ‘mixed crystal’ or ‘crystalline solid solution’ in relation to parallel compositions of Tl_(1−x)Rb_xNO₃.     

The ν3 and 2ν3 bands of SO3, SO3, SO3, and SO3

This sixth of a series of publications on the high-resolution rotation-vibration spectra of sulfur trioxide reports the results of a systematic study of the ν₃ and 2ν₃ infrared bands of the four symmetric top isotopomers ³²S¹⁶O₃, ³²S¹⁸O₃, ³⁴S¹⁶O₃, and ³⁴S¹⁸O₃. An internal coupling between the l=0(A₁^′) and l=2(E^′) levels of the 2ν₃ states was observed. This small perturbation results in a level crossing between |k−l|=9 and 12, in consequence of which the band origins of the A₁^′,l=0 “ghost” states could be determined to a high degree of accuracy. Ground and upper state rotational constants as well as vibrational anharmonicity constants are reported. The constants for the center-of-mass substituted species ³²S¹⁶O₃ and ³⁴S¹⁶O₃ vary only slightly, as do the constants for the ³²S¹⁸O₃, ³⁴S¹⁸O₃ pair. The S-O bond lengths for the vibrational ground states of the species ³²S¹⁶O₃, ³⁴S¹⁶O₃, ³²S¹⁸O₃, and ³⁴S¹⁸O₃ are, respectively, 141.981 99(1), 141.979 38(6), 141.972 78(8), and 141.969 93(8) pm, where the uncertainties, given in parentheses, are two standard deviations and refer to the last digits of the associated quantity.     

Lattice parameters variation with temperature of Ti2O3 and (Ti0.98V0.02)2O3 from single crystal X-ray data

The lattice parameters of Ti₂O₃ and (Ti_0.98V_0.02)₂O₃ have been measured as a function of temperature (24–670°C for Ti₂O₃ and 24–440°C for V-doped Ti₂O₃) from single crystal X-ray data. The high temperatures were attained by blowing hot argon directly on the crystal mounted on an automatic Philips diffractometer. This experimental set-up gives standard deviations which are at least 10 times better than those of the previous measurements and allows to keep Ti₂O₃ as such well above the transition. The variations of a, c, $\text{c}\text{a}$ (hexagonal axes) for pure Ti₂O₃ are in agreement with the previous results. On the contrary we did not observe any transition in the unit cell volume. The V-doping seems to attenuate the transition which is visible only on the a vs T curve     

Low temperature phase transition in the chain-like compounds NbSe3 and TaSe3

New transitions have been observed at low temperature by electrical measurements on the linear trichalcogenides NbSe₃ and TaSe₃. The resistivity of TaSe₃ drops near zero below 1.5 K which may indicate a superconducting transition. The resistivity of NbSe₃ drops below 2.2 K by 30 to 75% of its residual value at 4.2 K. However for TaSe₃ and NbSe₃ initial susceptibility measurements do not show any increase in diamagnetism indicating a flux expulsion. In addition the transitions below the critical temperatures are strongly non-linear with current density higher than 10^-3 A mm^-2.     

Brillouin scattering in KH3 (SeO3)2 above the transition temperature

The Brillouin scattering measurement in KH₃(SeO₃)₂ above the transition temperature shows a large anomaly in hypersonic velocity of the transverse wave with the wave vector q = [010] and the polarization ξ = [001], which indicates acoustic phonon softening.