Study of the CulCu2S system. conductivity of the solid solution Cu1+xI1−xSx(x<0.5)

A structural study of the CuICu₂S system has shown that a large solid solution ranges from pure CuI to Cu₃SI with a regular decrease of tehcell parameter ($\text{a=6.045 to 5.901}\text{A}\text{?}$); for richer Cu₂S concentrations, two-phase systems appear with the formation of a new Cu₇S₃I compound, and another solid solution exists for higher Cu₃S fractions (0.85<x<1). The ionic conductivity of the solid solution Cu_1+xI_1?xS_x (x<0.5) has been measured as a function of temperature between 54 and 307°C. The conductivity increases from 10^?7 ω^?1 cm^?1 (CuI) to 10^?3 ω^?1 cm^?1 (Cu_1.4I_0.6 S_0.4) at 25°C and then decreases until 10^?4 ω^?1 cm^?1 (Cu₃SI). In this last domain, no further phase transition occurs below the melting point and the low temperature γ phase can be considered as a stabilization of the high-conducting α phase. The variations of the conductivity are directly connected to those of the activation energy that decreases to a minimum value of 2.5 kcal mole^?1 for Cu_1.4I_0.6S_0.4.     

Pressure-induced H2 opacity in the 5-μm region

The H₂ opacity arising from the pure-rotational hexadecapole-induced U₀(J) transitions occurring during H₂H₂ and H₂He collisions, and from the hexadecapole-induced U₀(J) + S₀(J′) and the quadrupole-induced S₀(J) + S₀(J′) transitions in H₂He collisions, has been calculated. The U₀(J) and S₀(J) + S₀(J′) contributions from H₂H₂ collisions are important H₂ opacities in the frequency range from 700–3000 cm^?1 for temperatures appropriate to the outer planets. It is concluded that this opacity is needed in addition to the opacity from the extrapolation of the 0-0 and 1-0 H₂H₂ collisionally induced bands to interpret the spectrum at 5 μm for the outer planets.     

Electronic structure and magnetic properties of the compound CeCuIn

Magnetization, magnetic susceptibility, electrical resistivity, thermoelectric power and X-ray photoemission measurements were performed on a polycrystalline sample of CeCuIn. This compound crystallizes in a hexagonal structure of the ZrNiAl type. The magnetic data indicate that CeCuIn remains paramagnetic down to 1.9 K with a paramagnetic Curie temperature of −13 K and an effective magnetic moment equal to 2.5 μ_B. The electrical resistivity has metallic character, yet in the entire temperature range studied here, it is a strongly nonlinear function of temperature. The temperature dependence of the thermoelectric power is dominated by a small positive maximum near 76 K and a deep negative minimum at about 16 K. Above 150 K the thermopower exhibits a Mott's type behavior. The positive sign of the Seebeck coefficient in this temperature region indicates that the holes are dominant charge and heat carriers. The structure of Ce 3d_5/2 and Ce 3d_3/2 XPS spectra has been interpreted in terms of the Gunnarsson-Schönhammer theory. Three final-state contributions f⁰, f¹ and f² are clearly observed, which exhibit a spin-orbit splitting Δ_SO≈18.7 eV. The appearance of the 3d⁹f⁰ component is a clear evidence of the intermediate valence behavior of Ce. From the intensity ratio I(f⁰)/[I(f⁰)+I(f¹)+I(f²)] the 4f-occupation number is estimated to be 0.95. In turn, the ratio I(f²)/[I(f¹)+I(f²)]=0.08 yields a measure of the hybridization energy that is equal to 45 meV.     

Influence of Yb concentration on upconversion luminescence of Ho

Upconversion (UC) emissions at 360 ((⁵F, ³F, ⁵G)₂ → ⁵I₈), 392 (³K₇/⁵G₄ → ⁵I₈), 428 (⁵G₅ → ⁵I₈), 554 (⁵S₂/⁵F₄ → ⁵I₈), 667 (⁵F₅ → ⁵I₈) and 754 (⁵S₂/⁵F₄ → ⁵I₇) nm were obtained in 0.1 mol% Ho³⁺/x mol% Yb³⁺:Y₂O₃ (x = 2, 5, 8, 11, 15) bulk ceramics under infrared (IR) excitation at 976 nm. The intensity of the UC luminescence centered at 554 and 754 nm increased with Yb³⁺ concentration from 2 to 5 mol% and decreased from 5 to 15 mol%, while the UC luminescence centered at 392, 428 and 667 nm increased with Yb³⁺ concentration from 2 to 11 mol%, then started to reduce with Yb³⁺ concentration until 15 mol%. This comes from the competition between the energy back transfer (EBT) process [⁵S₂/⁵F₄(Ho) + ²F_7/2(Yb) → ⁵I₆(Ho) + ²F_5/2(Yb) as well as ⁵F₅(Ho) + ²F_7/2(Yb) → ⁵I₇(Ho) + ²F_5/2(Yb)] and spontaneous radiation process. The intensity of the UC luminescence centered at 360 nm always increases with Yb³⁺ concentration from 2 to 15 mol%. We believe that it may come from the cooperation of energy transfer process from Yb³⁺ ions in the ²F_5/2 state and the cross energy transfer process ⁵S₂/⁵F₄ + ⁵I₆ → (⁵F, ³F, ⁵G)₂ + ⁵I₈.     

Sublimation Study of Six 5-Substituted-1,10-Phenanthrolines by Knudsen Effusion Mass Loss and Solution Calorimetry

The vapor pressures of six solid 5-X-1,10-phenanthrolines (where X = Cl, CH₃, CN, OCH₃, NH₂, NO₂) were determined in suitable temperature ranges by Knudsen Effusion Mass Loss (KEML). From the temperature dependencies of vapor pressure, the molar sublimation enthalpies, Δ_cr^gH_m⁰(⟨T⟩), were calculated at the corresponding average ⟨T⟩ of the explored temperature ranges. Since to the best of our knowledge no thermochemical data seem to be available in the literature regarding these compounds, the Δ_cr^gH_m⁰(⟨T⟩) values obtained by KEML experiments were adjusted to 298.15 K using a well known empirical procedure reported in the literature. The standard (p⁰ = 0.1 MPa) molar sublimation enthalpies, Δ_cr^gH_m⁰(298.15 K), were compared with those determined using a recently proposed solution calorimetry approach, which was validated using a remarkable amount of thermochemical data of molecular compounds. For this purpose, solution enthalpies at infinite dilution of the studied 5-chloro and 5-methylphenantrolines in benzene were measured at 298.15 K. Good agreement was found between the values derived by the two different approaches, and final mean values of Δ_cr^gH_m⁰(298.15 K) were recommended. Finally, the standard molar entropies and Gibbs energies of sublimation were also derived at T = 298.15 K. The volatilities of the six compounds were found to vary over a range of three orders of magnitude in the explored temperature range. The large difference in volatility was analyzed in the light of enthalpies and entropies of sublimation. The latter was tentatively put in relation to the rotational contribution of the substituent group on the phenanthroline unit.     

Longitudinal magnetoresistance in zero-gap CdxHg1−xTe at low temperatures

The longitudinal magnetoresistance Δ?₆(H)/?₀ is studied experimentally in gapless solid solutions Cd_xHg_1?xTe (0 < x < 0.15) for temperatures 1.3–15 K and the electron concentrations n ～ 10¹⁵ cm^?3. The temperature and the magnetic field dependences of the observed negative longitudinal magnetoresistance are explained by the resonant nature of electron scattering by an acceptor level. The quantitative analysis of the $\text{Δ?6(H)}\text{?}{}_0$ field dependence for weak magnetic fields under strong carrier degeneracy makes it possible to evaluate parameters of the acceptor level involved.     

Investigation of the solid solution series 2(MnX)-CuInX2 (X=S, Se)

(2MnX)_x(CuInX₂)_1−x with X=S and Se were prepared by solid state reaction from the end members α-MnS, β-MnS and CuInS₂ in the range 0<x≤0.2 (≤0.6 for β-MnS) as well as MnSe and CuInSe₂ in the range 0<x≤0.1. Mixed crystals with 0≤x≤0.1 crystallize in the tetragonal chalcopyrite type structure, (2α-MnS)_x(CuInS₂)_1−x samples with 0.1<x≤0.2 and (2β-MnS)_x(CuInS₂)_1−x samples up to x=0.6 consist of two phases, occuring as tetragonal domains (x∼0.1 for X=S) within a cubic matrix with zinc-blende type structure (x∼0.4 for X=S), indicating a miscibility gap. For tetragonal single phase samples the band gap energy, the lattice constants and the anion parameter have been determined. The first and the latter ones show a different composition dependent behaviour caused by the modification of the MnS (α-MnS with NaCl type structure, β-MnS with zinc-blende type structure) used during the synthesis. Additionally a CuMn_xIn_1−xS₂ powder sample, in which Mn substitutes the M^III site, was investigated. The SQUID measurements revealed a well-distinct magnetic transition between 15 and 16 K as well as ferromagnetic-like hysteresis loops pronounced for temperatures below the transition temperature. Below this temperature a clear splitting between the zero field cooling (ZFC) and the field cooling (FC) curves indicate to the existence of a long-range magnetic ordering phenomenon. This behaviour was not found in the other samples were Mn substitutes both sites M^I as well as M^III.     

Effects of disorder and isotopic substitution in the specific heat and Raman scattering in LuB12

Precision measurements of the specific heat and spectral intensity I(ω) of Raman scattering for Lu ^N B₁₂ single crystal samples with various boron isotopes (N = 10, 11, nat) have been performed at low and intermediate temperatures. A boson peak in the low-frequency part of the I(ω) spectrum has been observed for the first time for lutetium dodecaboride at liquid nitrogen temperatures. It has been shown that low-temperature anomalies in the specific heat, along with the features of Raman spectra, can be interpreted in terms of the transition to a cageglass state at T* = 50?70 K, which appears when Lu³⁺ ions are displaced from the centrosymmetric position in cavities of a rigid covalent boron sublattice towards the randomly located boron vacancies. The concentrations of various two-level systems that correspond to two types of vibrational clusters with correlation lengths of 12–15 and 18–22 Å, respectively, have been estimated. The vibrational density of states of LuB₁₂ has been calculated from Raman spectra in the model of soft atomic potentials. An approach has been proposed to explain the dielectrization of the properties of the YbB₁₂ compound at T < T*, as well as the features of the formation of magnetic structures in RB₁₂ antiferromagnets (R = Tb, Dy, Ho, Er, Tm) and the suppression of superconductivity in LuB₁₂.     

Inhomogeneous broadening of the dynamically split Kramers spectral line and up-conversion in the pair and quartet centers in CaF2:Nd

The site-selective and time-resolved fluorescence laser spectroscopy and kinetic measurements with high spectral and nanosecond temporal resolution was applied to analyze the high-energy wing of the M and N absorption bands of the ⁴I_9/2(1)→⁴G_5/2(1) crystal-field (CF) transition in a CaF₂:Nd³⁺ (0.6 wt%) crystal at 4.2 K. It was found that at helium temperatures the dynamically split spectral line assigned as the ⁴I_9/2(1)→⁴G_5/2(1) (CF) transition of coherently coupled Nd³⁺ ions in the pair M- and quartet N-centers of CaF₂:Nd³⁺ (0.6 wt%) is inhomogeneously broadened. It consists of the pair M- and quartet N-centers with at least 0.1 A variation of the positions of the fluorescence-excitation spectral lines registered at the ⁴F_3/2(1)→⁴I_9/2(1) CF transition. Small fluorescence-lifetimes variation of the ⁴F_3/2 and ⁴D_3/2 levels from the small variation of the distances R between Nd³⁺ ions in the pair is found. At least 2.7% variation of the value of the Nd-Nd distance R in the pair M-center was determined from the lifetime variation of the ⁴F_3/2 manifold with the assumption of a dipole-dipole interaction between the ions in the pair.The energy transfer up-conversion process responsible for the UV fluorescence observed when pumping the ⁴I_9/2(1)→⁴G_5/2(1) transition has been determined.     

Separation of the ortho and para NMR signals in solid deuterium via DQ filtering

Double quantum (DQ) filtering is shown to lead to an effective separation of the NMR signals from the para (I = 1) and ortho (I = 2) molecules in solid deuterium. The separation is achieved by the pulse sequence 90_φ^°–t_pr–90_φ^°–t_ev–90_x^°–t, where the phase-cycled first two pulses create the DQ coherence. Two components are observed after the third pulse; the para signal shows the maximum at a short time t while the ortho signal reaches the maximum at a longer t. The observed signal can be expressed as ∑_I [F_I(t_pr − t) − F_I(t_pr + t)], where F_I(t) is a proper fitting function for the free induction signal of the para and ortho molecules (with I = 1 or 2, respectively). Numerical fits to experimental data at 4.2 and 2 K show that this method can be used to determine the ratio F₁(0)/F₂(0) and thus, because the initial value F_I(0) is proportional to the respective magnetization before the pulse sequence, the ortho and para concentrations in solid deuterium.     

Optical oxygen sensing materials based on trinuclear starburst ruthenium(II) complexes assembled in mesoporous silica

The preparation and oxygen sensing properties of optical materials based on two trinuclear starburst ruthenium(II) complexes: [Ru₃(bpy)₆(TMMB)]⁶⁺ (1) and [Ru₃(phen)₆(TMMB)]⁶⁺ (2) (bpy=2,2′-bpyridine, phen=1,10-phenathroline, TMMB=1,3,5-tris[2-(2′-pyridyl)benzimidazoyl]methylbenzene) assembled in two mesoporous silicate (MS) are described in this paper. The luminescence of Ru complexes/silicate assemble materials can be quenched by molecular oxygen with good sensitivity (I₀/I₁>5 for 2/MS and I₀/I₁>3 for 1/MS), indicating that trinuclear starburst Ru(II) complexes/MS systems are sensitive to oxygen molecules.     

Spin conversion rates in solid CH4Kr mixtures

Spin conversion rates in solid CH₄Kr mixtures have been measured at Kr concentrations up to 33% and 0.4 < T < 2K. The conversion rate increases by increasing the Kr concentration at constant temperature and increases weakly by decreasing the temperature at constant concentration.     

Determination of Oxygen partial free energy for non-stoichiometric TiO by E.M.F. measurements: Thermodynamics of TiO at 1323 K

The equilibrium oxygen partial pressures with non-stoichiometric TiO and the two phase regions TiOTi₂O₃ and Ti₂OTiO have been determined at 1323 K by electromotive force measurements with ThO₂Y₂O₃ solid electrolyte. These pressures are included between 10^?25.6atm and 10^?34.3atm. The results take into account the PO₂ dependence of the ionic transference number of our electrolytes. This dependence has been determined down to 10^?35 atm by using a UUO₂ reference electrode and applying a model proposed earlier by Schmalzried for the conductivity of ThO₂Y₂O₃.We had previously measured ΔH(O₂) for the same range of composition and at the same temperature. Hence a set of new thermodynamic data relative to ΔG(O₂), ΔH(O₂) and ΔS(O₂) is available for TiO at 1323 K.     

Ab initio study of phase stability,thermodynamic and elastic properties of C3N2 derived from cubic C20

In this work, we report a quite different conclusion from Tian et al. [Phys. Rev. B 78 (2008) 235431]. It is proved that β-C₃N₂ is the only phase under high pressure, and α-C₃N₂ does not exist. β-C₃N₂ is a covalent crystal composed of strong CC and CN covalent bonds. Band gap of β-C₃N₂ increases with pressure. The width of antibonding state, shown in partial density of states (PDOS), keeps about 5 eV with rising pressures, which brings stable CN or CC covalent bonds. At sufficiently low temperatures, heat capacity (C_v) is proportional to T³; and at intermediate temperatures, C_v is governed by the details of vibrations of the atoms; finally, C_v reaches to β-C₃N₂'s Dulong–Pettit limit (about 120 J/mol K). Though thermal expansion coefficient (α) increases with temperature, α is less than 1×10⁻⁵ K⁻¹. Elastic constants rise with pressure, but shear moduli is quite steady which increases just a little with pressures.     

Manganese-doped CdGeAs2, ZnGeAs2 and ZnSiAs2 chalcopyrites: A new materials for spintronics

Based on Mn-doped chalcopyrites CdGeAs₂, ZnGeAs₂ and ZnSiAs₂ the new dilute magnetic semiconductors with p-type conductivity were produced. Magnetization, electrical resistivity, magnetoresistance and Hall effect of mentioned compositions were studied. Their curves of temperature dependence of magnetization have the similar form in spite of complicated character, for which the concentration and mobility of the charge carriers are responsible. Thus, for T<15 K, these curves are characteristic for superparamagnetics and for T>15 K for a frustrated ferromagnetics. In compounds with Zn these two states dilute by spinglass-like state. This specific feature is assigned to an attraction of Mn ions occupying neighboring sites and to the competition between the carrier-mediated exchange and superexchange interactions. Curie temperatures of these compounds are above room temperature. These are the highest Curie temperatures in the A^IIB^IVC^V₂:Mn systems.     

Experimental investigation of muon-catalyzed dt fusion at cryogenic temperatures

An experimental investigation of muon-catalyzed fusion (μCF) in gaseous, liquid and solid mixtures of deuterium and tritium was performed. The target conditions included the range of densities of 0.03 ≲ φ ≲ 1.5, tritium concentrations of 2% ≲ c_t ≲ 90% and temperatures of 13 ≲ T ≲ 40K. The study was based on the analysis of observed cycling rates extracted from the measured time distributions of the fusion neutrons. For the first time, the density dependence of the rates λ_(dtμ)d⁰ for the dtμ molecule formation in collisions of tμ atoms in the lower (F=0) hyperfine state with D₂ molecules was determined experimentally. Evidence for the proposed effects of below-threshold resonances on molecular formation was found. Measurements at low temperatures in mixtures of different molecular compositions revealed a clear predominance of the λ_(dtμ)d⁰ formation rate. The probability q_1s for dμ atoms to reach the ground state was determined as a function of density and tritium concentration.     

Theoretical Study of the Dynamic Stark Effect on Dissociation of CsI

The influence of the dynamic Stark effect on the dissociation of CsI is theoretically studied by the time-dependent wave-packet method. After a pump pulse induces a dissociating wave packet that propagates through both the ionic channel X0⁺(Cs ⁺(¹ S ₀)?+?I ⁺(¹ S ₀)) and the covalent channel A0⁺(Cs(² S _1/2)?+?I(² P _3/2)), a Stark pulse is applied to control the diabatic-dissociation dynamics. The first-order non-resonant non-perturbative dynamic Stark effect gives control over the break up, the dissociation probabilities in the two channels being controlled by the delay between the pump and Stark pulses. With a 720-fs delay, the dissociation probability through channel A is greatly enhanced.