Conductivity of β″ and ion rich β alumina.I.H.+(H2O)n compounds

The conductivity and thermal stability of H⁺(H₂O)_n β″ and ion rich β alumina single crystals have been measured by the complex impedance method in the 25–700°C temperature range. Two mechanisms of conductivity were assumed: proton transfer at lower temperatures and H₃O⁺ diffusion in the high-temperature range. Both structures have similar properties, but ion rich β alumina possesses the best stability and the lowest activation energy (β: 0.15 eV, β″: 0.20 eV below 400 and 300°C respectively). The room-temperature conductivity is ≈5×10^?6 Ω^?1 cm^?1. The conducting properties and mechanisms are discussed and compared to other protonic or ionic conductors.     

Optical properties of Mn-activated Na2SnF6 and Cs2SnF6 red phosphors

Alkaline hexafluorostantanate red phosphors Na₂SnF₆:Mn⁴⁺ and Cs₂SnF₆:Mn⁴⁺ are synthesized by chemical reaction in HF/NaMnO₄ (CsMnO₄)/H₂O₂/H₂O mixed solutions immersed with tin metal. X-ray diffraction patterns suggest that the synthesized phosphors have a tetragonal symmetry with the space group D_4h¹⁴ (Na₂SnF₆:Mn⁴⁺) and a trigonal symmetry with the space group D_3d³ (Cs₂SnF₆:Mn⁴⁺). Photoluminescence (PL) analysis, PL excitation (PLE) spectroscopy, and the Raman scattering techniques are used to investigate the optical properties of the phosphors. The Franck-Condon analysis of the PLE data yields the Mn⁴⁺-related optical transitions to occur at ∼2.39 and ∼2.38 eV (⁴A_2g→⁴T_2g) and at ∼2.83 and ∼2.76 eV (⁴A_2g→⁴T_1g) for Na₂SnF₆:Mn⁴⁺ and Cs₂SnF₆:Mn⁴⁺, respectively. The crystal field parameters (Dq) of the Mn⁴⁺ ions in the Na₂SnF₆ and Cs₂SnF₆ hosts are determined to be ∼1930 and ∼1920 cm⁻¹, respectively. Temperature-dependent PL measurements are performed from 20 to 440 K in steps of 10 K, and the obtained results are interpreted by taking into account the Bose-Einstein occupation factor. Comprehensive discussion is given on the phosphorescent properties of a family of Mn⁴⁺-activated alkaline hexafluoride salts.     

Polarisation remanente dans les varietes de basse temperature de (NH4) 3AlF6 ET (NH4) 3FeF6

Dielectric and thermocurrent measurements have been carried out on (NH₄) ₃AlF₆ and (NH₄) ₃FeF₆ ceramic samples. A maximum of permittivity is observed close to the transition temperature (T_{T(NH4) 3AlF6} = 217K; T_T(NH43FeF6 = 264K. In the low-temperature phase a polarization current of about 10^-9A is obtained and can be reversed when the sign of the polarization field is changed, a property which could correspond to a ferroelectric behavior. However, no pyroelectric current is detected when the temperature decreases from T_T. Another hypothesis, based on a field-induced polarization, has been considered : the depolarization current could be due to charge displacements from potential minima favored by rising temperature. In any way, the low-temperature phase is characterized by a remanent polarization.     

Magneto-optical study of the 5ƒ2 → 5ƒ16d1 transition in UO2

High field Faraday rotation and magnetic circular dichroism measurements in the energy range between 1.4 and 5.4eV are reported for UO₂. The measurements are compared with two modified atomic models for the 5?² → 5?¹6d¹ transition using LS- and jj-coupling, respectively. Excellent agreement between theory and experiment is found only for a jj-coupling treatment of the final state.The Faraday rotation for magnetic saturation is estimated to be 3 × 10⁶ deg cm^?1 at 4.5 eV.     

Electrical conduction and 1ƒ noise in Li-DOPED MnO

Electrical resistivity, thermoelectric power and current noise were measured on Li-doped MnO single crystals in the temperature range from 300 to 1000 K. Below 700 K the crystals are p-type and the activation energy of the resistivity is 0.75 eV. Around 700 K the activation energy changes from 0.75 to 1.25 eV owing to a change from p- to n-type conduction. The depth of the Li acceptor is found to be 0.65 eV. From resistivity and thermoelectric power data it is concluded that the bandgap in first approximation can be written as E_s(T) = E_o ? γT between 750 and 1000 K, with E_o = 1.9 eV and γ = 6 × 10^?4 eV/K. The current noise spectra show $\text{1}\text{?}$ noise. The magnitude of the $\text{1}\text{?}$ noise is strongly temperature dependent. From the noise data it is deduced that E_o = 2.2 eV and γ = 10^?3 eV/K in the temperature range 430–700 K.     

Electron hopping mechanism in hematite (α-Fe2O3)

The frequency dependence of the real (?′) and imaginary (?″) parts of the dielectric constant of polycrystalline hematite (α-Fe₂O₃) has been investigated in the frequency range 0-100 kHz and the temperature range 190-350 K, in order to reveal experimentally the electron hopping mechanism that takes place during the Morin transition of spin-flip process. The dielectric behaviour is described well by the Debye-type relaxation (α-dispersion) in the temperature regions T<233 K and T>338 K. In the intermediate temperature range 233 K<T<338 K a charge carrier mechanism takes place (electron jump from the O²⁻ ion into one of the magnetic ions Fe³⁺) which gives rise to the low frequency conductivity and to the Ω-dispersion. The temperature dependence of relaxation time (τ) in the −ln τ vs 10³/T plot shows two linear regions. In the first, T<238 K, τ increases with increasing T implying a negative activation energy −0.01 eV, and in the second region T>318 K τ decreases as the temperature increases implying a positive activation energy 0.12 eV. The total reorganization energy (0.12-0.01) 0.11 eV is in agreement with the adiabatic activation energy 0.11 eV given by an ab initio model in the literature. The temperature dependence of the phase shift in the frequencies 1, 5, 10 kHz applied shows clearly an average Morin temperature T_Mo=284±1 K that is higher than the value of 263 K corresponding to a single crystal due to the size and shape of material grains.     

Étude par rmn de la localisation et des mouvements des protons dans les hydrures MgH2 et Mg2NiH4

Wide line and pulsed NMR studies are reported for MgH₂; and Mg₂NiH₄ hydrides at 79 and 30 MHz in the temperature range between 100 and 500 K. Line shape data confirm a rutile type structure for MgH₂, and lead to the evaluation that 97% of the hydrogen is present in this phase, the remainder being in solid solution MgH_x, (x<0.04).Mg₂NiH₄ shows a Gaussian line, whose peak-to-peak width decreases from 6.16 to 4.28 G in the range 320–365 K. From 365 to 480 K the spectrum shows a second, narrower, line (0.85 G), implying that approximately 7% of the protons have migrated from their initial position to energetically less stable sites. The thermal behaviour of the T₁ and T₂ relaxation times shows a dramatic variation in the 320–370 K temperature range in connection with the change of the proton localization. Relaxation mechanisms can be attributed mainly to conduction electron-nucleus interactions. With rising temperature, diffusion mechanisms are also involved. A diffusion activation energy of about 0.35 eV has been determined, with a diffusion coefficient 3.45 × 10^?8 < D < 4.6 × 10^?8 cm²/s.     

Molecular dynamics of [(CH2OH)3CNH3]2SiF6 by phase transition of 178 K

We have investigated the molecular motions of TRIS⁺ ([(CH₂OH)₃CNH₃]⁺) and ions in the [(CH₂OH)₃CNH₃]₂SiF₆ crystal below room temperature from the measurements of the spin-lattice relaxation time T₁ and the NMR absorption line of ¹H and ¹⁹F nuclei, in order to elucidate the changes of the molecular motions by the phase transition of T_c=178 K. The narrowing of the ¹⁹F-NMR line was observed around T_c=178 K and the reorientation of the anion appears above T_c. Moreover, from the analysis of the temperature dependence of T₁, we have observed that the activation energy of the reorientational motion of ions changes from 0.168 eV (T>T_c) to 0.185 eV (T<T_c). Based on these results, we found that the reorientational motion of ions is closely related to the origin of the phase transition at T_c. In addition, from the measurement of the ¹H-NMR line, we also found that the reorientational motion of H₂ in the -CH₂OH group becomes active accompanied by the phase transition.     

A variable temperature EPR study of the manganites (La1/3Sm2/3)2/3SrxBa0.33−xMnO3 (x=0.0, 0.1, 0.2, 0.33): Small polaron hopping conductivity and Griffiths phase

Four manganite samples of the series, (La_1/3Sm_2/3)_2/3Sr_xBa_0.33−xMnO₃, with x=0.0, 0.1, 0.2 and 0.33, were investigated by X-band (∼9.5 GHz) electron paramagnetic resonance (EPR) in the temperature range 4-300 K. The temperature dependences of EPR lines and linewidths of the samples with x=0.0, 0.1 and 0.2, containing Ba²⁺ ions, exhibit similar behavior, all characterized by the transition temperatures (T_C) to ferromagnetic states in the 110-150 K range. However, the sample with x=0.33 (containing no Ba²⁺ ions) is characterized by a much higher T_C=205 K. This is due to significant structural changes effected by the substitution of Ba²⁺ ions by Sr²⁺ ions. There is an evidence of exchange narrowing of EPR lines near T_min, where the linewidth exhibits the minimum. Further, a correlation between the temperature dependence of the EPR linewidth and conductivity is observed in all samples, ascribed to the influence of small-polaron hopping conductivity in the paramagnetic state. The peak-to-peak EPR linewidth was fitted to ΔB_pp(T)=ΔB_pp,min+A/Texp(−E_a/k_BT), with E_a=0.09 eV for x=0.0, 0.1 and 0.2 and E_a=0.25 eV for x=0.33. From the published resistivity data, fitted here to σ(T)∝1/T exp(−E_σ/k_BT), the value of E_σ, the activation energy, was found to be E_σ=0.18 eV for samples with x=0.0, 0.1 and 0.2 and E_σ=0.25 eV for the sample with x=0.33. The differences in the values of E_a and E_σ in the samples with x= 0.0, 0.1and 0.2 and x=0.33 has been ascribed to the differences in the flip-flop and spin-hopping rates. The presence of Griffiths phase for the samples with x=0.1 and 0.2 is indicated; it is characterized by coexistence of ferromagnetic nanostructures (ferrons) and paramagnetic phase, attributed to electronic phase separation.     

Phase transition of [(C6H5)3PCH3]+(TCNQ)-2 and electrical transport properties

The electrical conductivity at 10GHz, the dielectric constant, and the thermoelectric power (TEP) of [(C₆H₅)₃PCH₃]⁺(TCNQ)^-₂, from 230 up to 400 K, have been measured. This organic quasi-one-dimensional solid undergoes a first order phase transition at 314 K. At the transition the conductivity increases by a factor of 2.2 and the activation energy drops to 0.26 from 0.31 eV. At 314 K TEP decreases abruptly from -75 to -60μVK^-1 and remains almost constant for T > 314 K. The dielectric permeability ?₀ is constant and equal to 5 in the low temperature phase, increases abruptly by 7% at the transition, and then depends strongly on temperature in the high temperature phase. Results of the high temperature phase are interpreted in terms of a strongly correlated salt.     

Spin-state transition, magnetic, electrical and thermal transport properties of the perovskite cobalt oxide Gd0.7Sr0.3CoO3

The magnetization, resistivity ρ, thermoelectric power (TEP) S, and thermal conductivity κ in perovskite cobalt oxide Gd_0.7Sr_0.3CoO₃ have been investigated systematically. Based on the temperature dependence of susceptibility χ_g(T) and Seebeck coefficient S(T), a combination of the intermediate-spin (IS) state for Co³⁺ and the low-spin (LS) state for Co⁴⁺ can be suggested. A metal-insulator transition (MIT) caused by the hopping of σ* electrons (localized or delocalized e_g electrons) from the IS Co³⁺ to the LS Co⁴⁺ is observed. Meanwhile, S(T) curve also displays an obvious phonon drag effect. In addition, based on the analysis of the temperature dependence of S(T) and ρ(T), the high-temperature small polaron conduction and the low-temperature variable-range-hopping conduction are suggested, respectively. As to thermal conduction κ(T), rather low κ values in the whole measured temperature range is attributed to unusually large local Jahn-Teller (JT) distortion of Co³⁺O₆ octahedra with IS state.     

Optical,magneto-optical and mössbauer spectroscopy on Co3+ substituted cobalt ferrite Co2+Fe2−xCo3+xO4(0 ⩽ x ⩽ 2)

The magneto-optical spectra of Co_1+xFe_2?xO₄ show with increasing Co³⁺ content an increasing intensity of the 4A₂ ? 4T₁(F) and 4A₂ ? 4T₁(P) transition of Co²⁺ at 0.8 and 2.0 eV. A decrease in the Co²⁺-Fe³⁺ charge transfer transitions on octahedral sites is found. In the optical spectra a strong increase in optical absorption is found with dominant transitions at 0.8, 1.6 and 2.6 eV due to Co³⁺ crystal field transitions on octahedral sites and a Co²⁺-Co³⁺ charge transfer. Conversion Electron Mössbauer Spectroscopy has been used to determine the cation distribution in the surface layer of the samples. The results indicate a shift of Co²⁺ from octahedral to tetrahedral sites when Co³⁺ is substituted in CoFe₂O₄. This results in enhanced optical absorption, enhanced magneto-optical effects and a lower Curie temperature.     

Zr催化剂对NaAlH4和Na3AlH6可逆储氢性能的影响

采用基于密度泛函理论的平面波赝势方法,分别计算纯净的以及掺杂Zr的NaAlH₄和Na₃AlH₆的晶格结构常数、能量、电子局域函数和电子态密度.结果表明：NaAlH₄和Na₃AlH₆分别是带隙为46和31 eV的绝缘体;NaAlH₄和Na₃AlH₆中Al—H键是共价键,Na—H键是离子键;Zr原子替代Na原子 关键词： 储氢 4')" href="#">NaAlH₄ 3AlH₆')" href="#">Na₃AlH₆ Zr掺杂     

Transfert électronique d'intervalence entre sites inéquivalents: Étude de CaFe3O5 par spectrométrie Mössbauer

As in magnetite Fe₃O₄, calcium ferrite CaFe₃O₅ is an oxide in which electron transfer occurs between the iron ions ($\text{Fe}{}^{\mathrm{3+}}\text{Fe}{}^{\mathrm{2+}}\text{= 2}$). This intervalence exchange process has been studied by ⁵⁷Fe Mössbauer spectroscopy and by electrical conductivity measurements. In CaFe₃O₅, the Fe³⁺ and Fe²⁺ ions occupy different crystallographic sites and have a deformed octahedral coordination. Each Fe²⁺O₆ octahedron shares an edge with two Fe³⁺O₆ octahedra. In the antiferromagnetic region (T_N = 282 ± 2 K), the Fe³⁺ and Fe²⁺ ions are well differentiated. Thermally-activated electron transfer is observed above t_n, in the paramagnetic region and is well characterized by the Mössbauer spectra. These are analyzed using the hypothesis of an electron jump limited to a trimer Fe³⁺Fe²⁺Fe³⁺ which leads to a relaxation time of 180 ns at 298 K and 80 ns at 400 K. Within this temperature interval, the process follows the Arrhenius law with an activation energy of 0.10 eV. Electrical conductivity measurements lead to similar results with an activation energy of 0.09 ± 0.02 eV.     

Effects of Cr doping in bilayered manganite LaSr2Mn2O7: Resistivity, thermoelectric power, and thermal conductivity

Systematic studies of resistivity, thermoelectric power, and thermal conductivity have been performed on polycrystalline bilayered manganites LaSr₂Mn_2−xCr_xO₇ (0≤x≤0.2). It is found that the temperature dependence of both Seebeck coefficient S(T) and resistivity ρ(T) in the high temperature region follows the small polaron transport mechanism for all the samples. But in the low temperature region, variable-range-hopping (VRH) model matches the experimental data better. In addition, the maximum of absolute S(T) at low temperatures is gradually suppressed for the sample with Cr-doping level of x>0.04, implying that a new FM order probably arises. With decreasing the temperatures further, S(T) has a sign change and becomes positive for the sample with Cr-doping level of x>0.04, indicating that there may occur a variation of the type of charge carrier. As to thermal conduction κ(T), the low-temperature peak is suppressed due to Cr-doping. The variation of κ(T) is analyzed based on the combined effect due to the suppression of local Mn³⁺O₆ Jahn-Teller (JT) lattice distortion because of the substitution of Cr³⁺ ions for Mn³⁺ ions, which results in the increase in thermal conduction, and the introduction of the disorder due to Cr-doping, which contributes to the decrease in thermal conduction.     

Effects of Cr doping in electron-doped manganites La0.9Te0.1MnO3

The effects of Cr doping on Mn sites in the electron-doped manganites La_0.9Te_0.1MnO₃ have been studied by preparing the series La_0.9Te_0.1Mn_1−xCr_xO₃ (0.05≤x≤0.20). Upon Cr doping, both the Curie temperature T_C and magnetization M are suppressed. The resistivity measurements indicate that there exists a weak metal-insulator (M-I) transition for the sample with x=0.05, with an increase in the doping level, the M-I transition disappears and the resistivity increases. Thermopower S(T) exhibits a maximum near T_C for all samples. By fitting the S(T) and ρ(T) curves, it is found that the temperature dependences of both S(T) and ρ(T) in the high temperature paramagnetic (PM) region follow the small polaron conduction (SPC) mechanism for all samples. The fitting parameters obtained imply changes of both the average-hopping distance of the polarons and the polaron concentration with Cr doping in our studied samples. In the case of the thermal conductivity κ(T), the variation of κ(T) is analyzed based on the combined effects due to the suppression of the local Mn³⁺O₆ Jahn-Teller (JT) lattice distortion because of the substitution of Cr³⁺ for Mn³⁺ ions, which results in the increase in κ, and the introduction of the disorder due to Cr-doping, which contributes to the decrease in κ.     

Ionic conductivity and NMR relaxation study on Li3N single crystal

Both ionic conductivity and ⁷Li NMR relaxation time T₂ were studied on Li₃N single crystal samples containing an oxygen impurity. Owing to the O impurity, the samples showed a high ionic conductivity (σ⊥ = 0.83 S m^?1 and σ_∥= 0.013 S m^?1 at 300 K) and a low activation energy (E_a,⊥ = 0.19 eV and E_a,∥ = 0.24 eV). The intrinsic conduction accompanying vacancy generation within the Li₂N layer was observed in the high temperature region. In the extrinsic region only a motion of the Li ion located in the Li₂N layer is responsible for both σ_⊥ and σ_∥. The site exchange motion of two kinds of Li ion has little importance to the ionic conduction.     

Structure and electrical conductivity of a novel inorganic solid electrolyte: Na14.5[Al(PO4)2F2]2.5[Ti(PO4)2F2]0.5 (NATP)

A novel inorganic solid electrolyte with a layered framework structure stable up to 1043 K, Na_14.5[Al(PO₄)₂F₂]_2.5[Ti(PO₄)₂F₂]_0.5 (NATP), has been hydrothermally prepared and characterized by single-crystal and powder X-ray diffraction techniques, X-ray fluorescence (XRF) analysis, IR spectroscopic measurement, thermogravimetric and differential thermal analysis (TGA and DTA). NATP crystallizes in the acentric hexagonal space group P3 with a=10.448(2), b=10.448(2), , Z=1, containing a large number of Na⁺ cations in the interlamellar space and the cavities of its framework. There are six different crystallographic Na⁺ cationic sites, in which 8% Na(5) and 12% Na(6) sites are vacant. Electrical conductivity measurements show that Na⁺ cations exhibit a high mobility with two domains for the electrical conductivity versus temperature.     

EPR detection and study of new phase transitions in Mg(ClO4)2·6H2O

A temperature dependent EPR study of Mn²⁺ impurity-doped crystals of Mg(ClO₄)₂·6H₂O has led to the detection of two critical temperatures T₁ ~ 335K and T₂ ~ 324K where the EPR characteristics undergo distinct changes. The monoclinic distortion of the water octahedron around the metal ion shows little temperature dependence between T₁ and T₂ and T₂ and T₃ ~ 272K, while it is found to be comparatively strongly temperature dependent above T₁ and below T₃, decreasing as T approaches T₁ from the high temperature side and as T approaches T₃ from the low temperature side. At room temperature the water-perchlorate symmetry seems to deviate slightly from the perfect P6₃mc symmetry proposed from previous X-ray measurements by West. Although the space symmetry group of the unit cell appears to remain unchanged at T₁ and T₂, the temperatures T₁ and T₂ are suspected to be related to structural phase transitions in this crystal.     

BH2和AlH2分子的结构及其解析势能函数

运用二次组态相关(QCISD)方法，分别选用6-311++G(3df,3pd)和D95(3df,3pd)基组，对BH₂和AlH₂分子的结构进行了优化计算，得到BH₂分子的稳态结构为C_2v构型，电子态为²A₁、平衡核间距R_BH=0.1187nm、键角∠HBH=128.791°、离解能D_e=3.65eV、基态振动频率ν₁(a₁)=1020.103cm^-1,ν₂(a₁)=2598.144cm^-1,ν₃(b₂)=2759.304cm^-1.AlH₂分子的稳态结构也为C_2v构型，电子态为²A₁、平衡核间距R_AlH=0.1592nm、键角∠HAlH=118.095°、离解能D_e=2.27eV、基态振动频率ν₁(a₁)=780.81cm^-1,ν₂(a₁)=1880.81cm^-1，ν₃(b₂)=1910.46cm^-1.采用多体项展式理论推导了基态BH₂和AlH₂分子的解析势能函数，其等值势能图准确再现了BH₂和AlH₂分子的结构特征及其势阱深度与位置.分析讨论势能面的静态特征时得到BH+H→BH₂反应中存在鞍点，活化能为150.204kJ/mol；AlH+H→AlH₂反应中也存在鞍点，活化能为54.8064kJ/mol. 关键词： 2')" href="#">BH₂ 2')" href="#">AlH₂ Murrell-Sorbie函数 多体项展式理论 解析势能函数