Thermodynamic properties of the CeSn3 mixed valence compound

We have measured on the CeSn₃ compound, the expansion coefficient between 80 and 800 K at normal pressure, the isothermal compressibility in the 0–8 GPa pressure range at room temperature and the heat capacity at constant pressure in the 60–300 K temperature range. The experimental data were compared with those previously found for the isomorphous LaSn₃ phase, assumed as a proper reference material for the study of the intermediate valency states in CeSn₃. Both the thermal expansion (3α) and the isothermal compressibility (k) of CeSn₃ show behaviours quite different from those of LaSn₃: for instance, in the standard conditions, 3α is 55 × 10^?6K^?1for CeSn₃ and 38 × 10^?6K^?1for LaSn₃; k is 15 × 10^?12 Pa^?1 and 12 × 10^?12 Pa^?1 respectively for CeSn₃ and LaSn₃. The thermal behaviour of the molar specific heat at constant pressure of CeSn₃ is similar to that of LaSn₃ for temperatures lower than 50 K. In the 70–300 K temperature range, the heat capacity of CeSn₃ is clearly higher than that of LaSn₃, ΔC_p being maximum near 150 K. The analysis of the calorimetric data show that the electronic coefficient γ of CeSn₃ is temperature dependent: its value varies from 53 mJ K^?2 mole^?1 at low temperature 24 mJ K^?2 mole^?1 at 300 K.     

Anomalous temperature dependence of the energy gap of AgGaS2

The lowest energy gap Eg of AgGaS₂ in the temperature range from 4.2 to 300° K was determined from the reflectivity, photoluminescence and absorption measurements. Below ～ 80° K the temperature coefficient of the energy gap is +6 × 10^-5eV/°K. Above ～80° K the sign of the coefficient reverses and the value is -1.8 × 10^-4eV/°K. The positive value is explained with the lattice dilation effect being the dominant mechanism for the energy gap variation at lower temperatures than ～80°K.     

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.     

Proton-induced F-centers in LiF and MgF2

The growth of F-centers in LiF irradiated at room temperature with 40- and 85-MeV protons and with ⁹⁰Sr electrons was found to be proportional to the square root of the absorbed energy over the range 0.5 to 2.3 Mrad which corresponds to an F-center density range of 1 × 10¹⁶ to 1.5 × 10¹⁷ per cm³. The production efficiency was 5 × 10³eV per F-center at an absorbed energy of 2.3 Mrad. The density of F-centers produced in MgF₂ by 40- and 85-MeV protons was measured over an absorbed energy range of 0.2 to 29 Mrad which corresponds to a maximum F-center density of 2 × 10¹⁶ per cm³. The production efficiency for MgF₂ was 4 × 10⁵eV per F-center at an absorbed energy of 16 Mrad.     

Cross sections for slow ion production and charge transfer in H+3(D+3)−H2(D2) collisions

Slow ion production cross sections for collisions of H⁺₃ and D⁺₃ ions with H₂ and D₂ have been measured at collision energies between 100 eV and 500 eV. The values vary from 2 × 10^-17 cm² to 6 × 10^-17 cm². The smaller cross sections for D₃ projectiles may be explained as an internal energy effect.     

Van Vleck paramagnetism of the thulium garnet Tm3Al5O12

The magnetic susceptibility of the garnet-type single crystal Tm₃Al₅O₁₂ exhibits the typical Van Vleck temperature independent paramagnetism below ≈8 K. The temperature dependence of the susceptibility over the range 2.0-300 K has been analyzed on the assumption that the cubic crystal-electric-field dominates the energy level on ³H₆ (J=6) ground multiplet for Tm³⁺ ion having 12-electrons in 4f shell. The ground state of the ³H₆ is nonmagnetic with Γ₂ singlet, avoiding the Kramers doublet. The energy separation between Γ₂ and the first excited state Γ⁽²⁾₅ triplet is evaluated to be 68.0 K. The whole energy interval Δ between Γ₂ and the highest state Γ₁ in ³H₆ is estimated to be 339.5 K.     

Critical behaviour of a uniaxial ferromagnet,ErCl3·6H2O with predominant dipolar interactions

The parallel magnetic susceptibility χ of a uniaxial ferromagnet ErCl₃·6H₂O has been measured between 0.3 and 4.2K and specially near T_c = 0.353 K. The predominant contribution to the Curie-Weiss temperature is due to the dipolar interactions. χ is proportional to ?^?γ with $\text{? =}\text{T}\text{T}{}_{\mathrm{c}}\text{?1}$ in the range 10^?3 < ? < 5 × 10^?2. The γ value, γ = 1.01 ±0.03 is consistent with the theoretical prediction for a uniaxial dipolar ferromagnet.     

Magnetostriction measurements of CoS2 single crystal

The magnetorestriction constants of CoS₂ single crystal were measured by a capacitance method in a temperature range from liquid N₂ to the Curie temperatures.The constants γ₁₀₀ and γ₁₁₁ are ?1.9 × 10^?6 and 5.7 × 10^?6 at liquid N₂ temperature respectively, and the absolute values of the constants decrease monotonically with the increase of the temperature. The volume magnetorestriction constant δω/δH at 110 K in the ferromagnetic state is 6 × 10^?10 Oe^?1.     

The adsorption of CO,O2, and H2 on Pt(100)-(5×20)

The adsorption/desorption characteristics of CO, O₂, and H₂ on the Pt(100)-(5 × 20) surface were examined using flash desorption spectroscopy. Subsequent to adsorption at 300 K, CO desorbed from the (5×20) surface in three peaks with binding energies of 28, 31.6 and 33 kcal gmol^?1. These states formed differently from those following adsorption on the Pt(100)-(1 × 1) surface, suggesting structural effects on adsorption. Oxygen could be readily adsorbed on the (5×20) surface at temperatures above 500 K and high O₂ fluxes up to coverages of $\text{2}\text{3}$ of a monolayer with a net sticking probability to ssaturation of ? 10^?3. Oxygen adsorption reconstructed the (5 × 20) surface, and several ordered LEED patterns were observed. Upon heating, oxygen desorbed from the surface in two peaks at 676 and 709 K; the lower temperature peak exhibited atrractive lateral interactions evidenced by autocatalytic desorption kinetics. Hydrogen was also found to reconstruct the (5 × 20) surface to the (1 × 1) structure, provided adsorption was performed at 200 K. For all three species, CO, O₂, and H₂, the surface returned to the (5 × 20) structure only after the adsorbates were completely desorbed from the surface.     

Absorption spectra of C6H6 and C6D6 near 340 nm

The absorption spectra of C₆H₆ and C₆D₆ in the liquid phase have been studied near 340 nm. The absorption spectrophotometric mounting was a sequential double-beam attachment with linear response to energy on scanning of the spectrum before the exit slit and an electronic device which gives directly either the absorbance or the integrated absorbance of a transition and, consequently, its oscillator strength.The oscillator strength measured for the band of C₆H₆ is 8×10^?8, which corresponds to a dipole moment of 2.4×10^?3 Debye; this value is of the same order as a theoretical value calculated by Tsubomura and Mulliken (3.8×10^?3 Debye) for a transition between states ³F and ³A of an oxygen-benzene pair. This agreement corroborates the hypothetical existence of such a transition.The first vibrational band is at 28553 cm^?1 for C₆H₆; this band is not observed in the vapor or solid phase. It corresponds probably to the transition 0-0, which is considered in the literature to be near 29500 cm^?1. The isotopic shift measured for this first band is 164 cm^?1. The vibrational frequencies are, respectively, 910 cm^?1 for C₆H₆ and 889 cm^?1 for C₆D₆.     

Electrical transport measurements in a quasi-onedimensional semiconductor ZrS3

We have used the technique of chemical vapour transport to prepare needle shaped single crystal of ZrS₃. Results of the measurements of d.c. resistivity. Hall coefficient and thermoelectric power of the temperature range 100–500 K are reported. All the samples exhibited semiconducting behaviour with a room temperature resistivity of about 15 Ω-cm and an activation energy of 0.20±0.02 eV. Room temperature thermoelectric power is -850 μVK^?1 and the dominant carriers are electrons. The thermoelectric power varies as (1/T), a behaviour associated with a typical semiconductor. Mobility at low temperatures is limited by ionized impurity scattering and is given by μ₁ = 6.5 × 10^?2T^3/2 cm²V^7-1 sec^?1. At high temperatures, phonon scattering is dominant and the mobility is given by μ₂ = 1.35 × 10⁺⁵T^?32 cm²V^?1 sec^?1.     

Magnetic properties of the garnets Bi0·8Ca2χT2·2-2.χFe5-χVχ]O12

The behaviour of the magnetization, Curie temperature, Mössbauer spectra, and lattice parameter is studied in the garnet series Bi_0·8Ca_2.χT_2·2-2.χFe_5-χV_χ]O₁₂. The shape of magnetization vs temperature curves shows only a minor dependence on x. The hyperfine field at the octahedral ⁵⁷Fe nuclei at 5°K decreases linearly with x (12·5kOe per substituted V neighbour), while that at the tetrahedral ⁵⁷Fe nuclei is not affected. The dependence of the Curie temperatures and hyperfine fields on x is discussed in relation to the Fe-O-V-O-Fe exchange. The influence of Bi substitution is consistent with the idea of a geometric effect.     

Crystal growth,structure, electron paramagnetic resonance and magnetic properties of (NH4)2V3O8

A method to grow single crystals of ammonium vanadate (IV, V) (NH₄)₂V₃O₈ has been devised. The crystal structure is tetragonal P4bm; residual factor is R = 0.030. Cell parameters are $\text{a = 8.891 ± 0.004}\text{A}\text{?}$ and $\text{c = 5.582 + 0.002}\text{A}\text{?}$. The V⁵⁺ atom lies at the center of a triangular pyramide (VO₄ tetrahedron) while the V⁴⁺ atom is on A 4-fold rotation axis at the center of a square-based pyramide VO₅ whose symmetry point group is almost C_4v with the short V = O bond lying along the 4-fold axis parallel to the c edge of the tetragonal cell. Crystals are thin platlets with (001) cleavage planes. The platlets have very often a square or rectangular shape limited by {100} or {110} planes. Each single crystal was not large enough to record a good e.p.r. spectrum, but by sticking on the same quartz plate a score of them it was possible to gather enough crystals so to record correct spectra and by orienting the plate to obtain resonance lines separately for g_∥ = 1.9263 et g_τ = 1.9755. Measurements at 283 K on powder samples gave times for spin-spin relaxation T₂ = 0.4 × 10^?7s and for spin-lattice relaxation T₁ = 1.6 × 10^?7s. The magnetic structure is characterized by an exchange narrowing ω_e = 3 × 10¹⁰rad/s which corresponds to a transition temperature of about 0.5 K. Static susceptibility measurements at high magnetic field show a paramagnetic behaviour with an antiferromagnetic interaction which is interpreted in the magnetic space group P_2c4bm as the interaction between V⁴⁺ ions from consecutive planes parallel to (001).     

Magnetic annealing and crystallization kinetics of the metallic glass Fe5Co70Si15B10

Magnetic annealing and crystallization kinetics of amorphous ribbons of Fe₅Co₇₀Si₁₅B₁₀ were studied. For a toroid stress-relieved at 365°C for 2 h, the anistropy energy K_u obtained by cooling in a magnetic field from 300°C was ≈1.1 × 10³erg/cm³ at room temperature. The reorientation of induced anisotropy of this toroid followed the equation for first-order kinetics closely, yielding an activation energy ΔE = 1.9 eV and a pre-exponential frequency factor v₀ = 3.2 × 10¹³s^-1. Anisotropy reorientation in a toroid partially stress-relieved at 220°C, although was clearly reversible during 8 cycles of isothermal annealing in tranverse and in longitudinal field, exhibited significant deviations from the equation for first order kinetics. Treating the data in terms of the equation for first order kinetics, a narrow spectrum of activation energy from 1.2 to 1.8 eV, with corresponding frequency factors from 1.8 × 10⁸ s^-1 to 5.6 × 10¹² s^-1, was obtained. The difference in behavior between the two samples is discussed in the light of concepts in structural relaxation recently proposed by T. Egami. Crystallization kinetics was studied on a DSC apparatus, using Kissinger's method. At 10 K/min heating rate, the temperature of incipient crystallization was found to be 770 K. The activation energies found were in the range 4.8–4.2 eV.     

Hall effect of a linear-chain metal: NbSe3

We present measurements of the low-field Hall constant R_H as a function of field and temperature in the linear-chain metal NbSe₃, The data range from 2 K to 200 K in temperature and up to 15 kG in field. At the two phase transitions T₁ (142 K) and T₂ (58 K) R_H shows an abrupt increase in magnitude but no change in sign. Below 30 K R_H becomes strongly field dependent. The zero-field-limit R_H changes from n-type to p-type at 15 K. It is argued that the results are consistent with a two-band model in which the difference in population p - n is equal to 3 × 10¹⁸ cm^-3 below T₂. The hall data are also consistent with a model in which both a loss of carriers and a drastic change in the conductivity anisotropy occur at T₁ and T₂ and lend support to the charge-density-wave hypothesis which has been used to characterize the two transitions.     

Fluorescence enhancement of Eu3+ by Tb3+ in dimethylsulfoxide (DMSO)

Photoexcitation of EuCl₃.6H₂O and TbCl₃.6H₂O mixtures in DMSO at various wavelengths brings about a decrease in the fluorescence intensity of Tb³⁺ and a subsequent enhancement in the fluorescence intensity of Tb³⁺ provided that [Tb³⁺] < [Eu³⁺]. The average value of the electronic excitation energy transfer rate constant k₁₀ which was found to be independent of the excitation wavelength, was determined to be about 1.50 × 10³ M^-1 s^-1. Photoexcitation of Tb³⁺ and subsequent population of high energy excited states is accompanied by rapid nonradiative de-excitation processes to the lowest excited state ⁵D₄, which is the origin of the energy transfer process. A lower limit for the value of the reaction rate constant, associated with the transition ⁵D₃ ? ⁵D₄, namely k₅, is of the order of 10⁵ ?10⁶ s^-1. Excitation at conditions leading to the exclusive population of the ⁵D₄ state of Tb³⁺ gave rise to a value of k₁₀ equal to (2.2 ± 0.4) × 10³ M^-1 s^-1 and a critical separation (R₀)_exp between Tb³⁺ and Eu³⁺ of about 13 Å. A theoretical value of R₀ equal to 14.2 Å was calculated. The energy transfer process does not appear to take place via clear cut dipole-dipole interactions but rather via complex multipole and/or exchange interactions.     

Thermal expansion of lT-TaS2 and 2H-NbSe2

The thermal expansion of the a and c axes of lT-TaS₂ and of the a axis of 2H-NbSe₂ have been measured between 4 K and 360 K. Discontinuities in the lattice parameters of TaS₂ were observed at the known charge density wave phase transitions near 200 K and 352 K, and a new transition was found near 283 K. These results are used to estimate the entropy changes occurring at the phase transitions. At the charge density wave onset temperature in NbSe₂ we find an upper limit to any discontinuity in the a axis of 2 × 10^-7 and to any discontinuity in the expansion coefficient of 3 × 10^-7 K^-1.     

Optical band-gap of Zn3As2

Absorption measurements of single Zn₃As₂ crystals were made at temperatures 5, 80 and 300 K. Free-carrier absorption is interpreted in the simple classical model. Interband absorption shows contributions from Urbach-like excitations. The direct optical gap has been estimated as 0.99 eV at 300 K, 1.09 eV at 80 K and 1.11 eV at 5 K. The linear dependence of band-gap on temperature was found in the range 80–300 K with dE_g/dT = ? 4.55 × 10^?4eVK^?1.     

Some thermomagnetic transport effects of Cd3P2

In this paper for the first time measurements are presented of the transverse Nernst effect, the Righi-Leduc effect and the Maggi-Righi-Leduc effect in cadmium phosphide. The measurements were performed on unoriented Cd₃P₂ single crystals, with electron concentrations in the range 0.05–1.7 × 10²⁴m^?, at 110 and 300 K in magnetic fields up to 1.8 $\text{Wb}\text{m}{}^2$. We also measured the room temperature dependence of the zero-field Seebeck coefficient on electron concentration of a large number of undoped and Cu-doped samples. A reversal of sign of the transverse Nernst effect was observed at an electron concentration of about 1.2?1.5 × 10²⁴ m^?3. This reversal of sign and the zero-field Seebeck coefficient vs electron concentration for undoped material can be quantitatively described by a Kane-type conduction band with ?_g = 0.50 eV, m¹_e = 0.040 m_o and a scattering parameter r = ?1. (Optical phonon scattering, if interpreted in a single mode.) This strongly confirms the results of Radautsan et al. that Cd₃P₂ has a non-parabolic Kane-type conduction band. The Righi-Leduc and Maggi-Righi-Leduc effect measurements at 110 K on samples with high electron concentrations, yielded Lorenz numbers only half their theoretical values, indicating that the electron scattering contains an inelastic contribution.     

Current induced deformation of charge density waves in orthorhombic TaS3

The low electric field ohmic resistance R of orthorhombic TaS₃ measured at 90 and 120 K well below the Peierls transition temperature depends on the product of a temperature difference ΔT applied along the sample and the sign of a previously applied current pulse if this pulse is larger than threshold for non-ohmic conductivity. This resistance change is about ΔR/RΔT ∽ 1×10^-3 K^-1 for a pure sample and ΔR/RΔT ∽ 6×10^-3 K^-1 for a slightly electron irradiated one at 90 K. The relative resistance change is insensitive to the sample length. We deduce that the CDW current changes inhomogeneously the Peierls gap E_g. ΔE_g < O at the contact where the CDW current enters and ΔE_g > O at the exit. The effect is attributed to a CDW current induced inhomogeneous deformation of the CDW itself.