Quantum mechanical relations in interface processes at electrode systems of the second kind

It is shown that the difference of the electrochemical standard potentials between Ag/AgCl(s), KCl (aq, a = 1 mole l⁻¹) and Ag/AgBr(s), KBr (aq, a = 1 mole l⁻¹ can be attributed to the ion exchange from the AgCl phase to the AgBr phase. In this process, quantum mechanical relations play an essential part. A relation derived from Einstein's equation for calculating the inner energy of an ionic crystal and from the AC-Josephson equation allows the calculation of the difference of the electrochemical standard potentials between the electrode systems Ag/AgCl(s), Cl⁻-Ag/AgBr(s), Br⁻; Cu/CuCl(s), Cl⁻-Cu/CuBr(s), Br⁻ and Hg/Hg₂Cl₂(s), Cl⁻-Hg/Hg₂Br₂(s), Br⁻ from the frequency of the longitudinal optical phonons. An equation for the quantum mechanical calculation of the nernst factor (RT/zF) in the so-called Nernst equation is given. Thus, the structural parameters of the respective solid state electrodes are in close relation with the transport processes in electrode systems of the second kind.     

Propagation of acoustic waves in crystals of univalent mercury halides

Sections through the surfaces of phase and group velocities of propagation of acoustic waves in Hg₂Cl₂, Hg₂Br₂ and Hg₂I₂ were ascertained. The relations between the directions of energy propagation and the directions of phase velocities were also established. It was found that the energy flux deviates from the A-plane towards the [001] direction. The direction of the smallest velocity of propagation of acoustic waves in the A-plane was found, too. The results of this study are interesting especially with respect to the practical utilization of some new types of acoustic and acousto-optic elements.     

Contribution to the study of elastic properties of KGd(WO4)2:Er3+ single crystals by Brillouin spectroscopy

In this paper we present the study of the acoustic phonons propagating in Er³⁺‐doped KGd(WO₄)₂ single crystals by Brillouin spectroscopy. For the investigated crystals the velocities of the longitudinal and transverse acoustic phonons [100], [010], [001], [101] and [110] have been determined. Moreover, the values of the elastic constants: C₂₂, C₄₄ and C₆₆ of Er³⁺‐doped KGd(WO₄)₂ single crystals have been estimated. It was revealed that the presence of the Er³⁺‐ions in KGd(WO₄)₂ crystals, for the used doping concentration 1 at% does not influence their elastic properties. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation of radiation defects in electron irradiated Hg1−xCdxTe crystals using positron annihilation

The electron characteristics of defects in the initial and electron irradiated Hg_1−xCd_xTe (2–3 MeV, 10¹⁸ cm⁻², 300 K) crystals using the positron annihilation method have been investigated. The data of electric measurements are confirmed on connection of p-type conductivity with vacancy defects of metal sublattice initial crystals Hg_1−xCd_xTe. An analysis of correlation curves of irradiated crystals has shown a possibility of formation of associations of initial defects and radiation damages of vacancy type during radiation process. The presence of narrow component on correlation curves in the region of small angles is associated with formation of positronium states localized in the region of radiation defect complex of vacancy type. Identification of positron-sensitive defects with electrically active radiation induced ones has been carried out according to the results of isochronal annealing of irradiated crystals.     

Elastic properties of KGd(WO4)2:Ho3+ single crystals studied by Brillouin spectroscopy

The analysis some of the acoustic phonons propagating in pure and Ho³⁺‐doped KGd(WO₄)₂ single crystals in the GHz frequency range by Brillouin scattering method has been presented. For investigated crystals the velocities of the longitudinal and transverse acoustic phonons [100], [010], [001], [101], [101] and [110] have been determined. Moreover, the value of elastic constants C₂₂, C₄₄ and C₆₆ of pure and Ho³⁺‐doped KGd(WO₄)₂ single crystals have been estimated. It was revealed that the presence of the Ho³⁺‐ions in KGd(WO₄)₂ crystals, for the used doping concentration 1 at% and 8 at%, does not influence their elastic properties. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

X-Ray Diffuse Scattering Study of Anisotropy of Elastic Properties in Silver Thiogallate

Measurements of the diffuse X-ray scattering intensity are performed from the (100) and (001) planes in the AgGaS₂ compound with tetragonal chalcopyrite-type structure. From these data the phase velocities of elastic waves along the principal symmetry directions for longitudinal and transverse polarizations as well as all six elastic moduli C_ik are found. The comparative analysis of both the anisotropy of the thermal diffuse scattering intensity distribution and the character of the elastic anisotropy for the ternary compound AgGaS₂ with the chalcopyrite structure and the binary analogs CdS and ZnS with the sphalerite structure is carried out.     

Microhardness of single crystals of the calomel family

Microhardness of Hg₂Cl₂, Hg₂Br₂ and Hg₂I₂ single crystals has been measured on (001) and (110) faces using the indenter after Vickers. It has been found that the microhardness of the first two homologues differs only slightly whereas the iodide is considerably softer: by about 20% on the (001) face and by about 30% on the (110) face. The average microhardness value, calculated from the values obtained on gradually rotating the indenter over 360° on the (001) face, is for Hg₂Cl₂ and Hg₂Br₂ practically equal to the microhardness of NaCl (20.3 and 19.4 compared to 19.6 · 10⁷ Pa). The average microhardness of the (110) face is for Hg₂Cl₂ and Hg₂Br₂ about 2 × lower and for Hg₂I₂ about 2.6 × lower than that of the (001) face. In the case of Hg₂Cl₂ the microhardness of the (001) face has been also calculated from crystallochemical parameters and the results have been found to be in good agreement with the value obtained experimentally for the orientation of the indenter's diagonal parallel to the [100] direction, where the data is the least influenced by the elasticity of the sample (16.6 compared to 18.6 · 10⁷ Pa).     

The growth of HgI2 crystals

The paper presents a system for αHgI₂ crystal growth by the temperature oscillation method. The system has a capability of crystal growing at an excess I₂ or Hg vapour pressure. Optimum conditions for producing crystals up to 2 cm³ by volume have been established. The crystals grown at an excess I₂ vapour pressure have higher resistivity and higher drift electron and hole mobilities — μ_e = 120 cm² V⁻¹ s⁻¹ and μ_h = 6 cm² V⁻¹ s⁻¹, respectively.     

Growth and Characterisation of Gel-grown Lead(II)Chloride and Lead(II)Bromide Single Crystals

Single crystals of pure and doped lead(II)chloride and lead(II)bromide were grown by gel technique employing a modified two-stage chemical reaction. Methods to minimise the predomination of needle morphology during the growth of these crystals have been investigated and the results are discussed. The grown crystals were characterised by optical transmission spectrum. Undoped and monovalent cation (K⁺, Na⁺, Cu⁺, Ag⁺ and Hg⁺) doped crystals of PbCl₂ and PbBr₂ were subjected to d.c. electrical conductivity studies. Using the log σT versus T⁻¹ plot, the activation energies for the migration of anion vacancies in lead(II)halides are calculated. They are found to be less for the doped crystals than those of undoped ones.     

Crystal structure of marmesin,C14H14O4, 2-(β-hydroxyisopropyl)-2,3-dihydro-6,7-furano-coumarin

The unit cell parameters of this compound were determined by least-squares calculations from the adjusted angular setting of 25 general reflections. The crystals are monoclinic with the following crystallographic data: a = 5.718(1), b = 13.794(4), c = 7.861(1) Å, β = 100.53(2)°, Z = 2 and D_x = 1.34 g · cm⁻³. The space group according to the systematic absences is P2₁. The structure of this compound was solved by direct methods and refined by full matrix least-squares with anisotropic temperature factors to R = 0.04. The refined atomic positions indicate a considerable strain within the molecule. The structure is built up from molecules connected by H-atoms forming infinite chains along b-axis.     

Effect of change of state of aggregation of impurity on tl and microhardness of KClxBr1–x mixed crystals doped with Ca2+

Microhardness and Thermoluminescence (TL) measurements have been made in KCl_xBr_1–x mixed crystals doped with Ca²⁺ impurity. The variation of hardness in undoped and Ca²⁺ doped KCl_xBr_1–x crystals with quenching temperature is investigated. TL studied of KCl_xBr_1–x crystals doped with Ca²⁺, both in as-grown state and after quenching them from various elevated temperatures indicate that the positions of the glow peak which has been attributed to F-centers is found to depend upon the state of dispersion of impurity.     

Elastic,Piezoelectric and Dielectric Constants of Pentaerythritol

The elastic, piezoelectric and dielectric constants of pentaerythritol, C(CH₂OH)₄, have been computed employing the method of long waves and the unscreened rigid ion potential model developed by RAMAMOORTHY and KRISHNAMURTHY. Piezoelectric contribution is taken into account in the computation of elastic constants. This is the first report on the piezoelectric and dielectric constants of pentaerythritol. In the notations followed by LANDOLT-BORNSTEIN the computed piezoelectric constants are: _g14 = 4.82, _g15 = 4.37, _g31 = 16.21 and _g36 = 5.89 (in unit of 10⁻¹Vm/N) and the static dielectric constants are: K₁ = 2.38 and K₃ = 2.47. The hydrogen bonding in pentaerythritol has no effect on its dielectric behaviour. Calculation of acoustic velocities in piezoelectric crystals and as a special case to the crystals of class 4 is explained in detail. Sound velocities calculated from the elastic, piezoelectric and dielectric constants computed in the present investigation agree with the experimental values determined by the ultrasonic method.     

Acoustic study of elastic properties,dislocation damping and plasticity of crystals

The results of acoustic studies of elasticity and dislocation inelasticity of crystals are presented. Regularities of elastic anisotropy variation with ionicity of bonds in A_NB_8-N crystals have been considered. Amplitude dependences of ultrasound damping supply the information on dislocation structure and dislocation — to point defect interaction. Oscillation of dislocations during internal friction measurements are compared to their translation motion at the onset of plastic flow.     

Electric Characterization of Indium Sesquiselenide Single Crystals

Conductivity, Hall-effect measurements were performed on δ-phase In₂Se₃ single crystals, grown by the Bridgman method over the temperature range 150–428 K, in the directions perpendicular and parallel to the c-axis. The anisotropy of the electrical conductivity and of the Hall coefficient of n-type In₂Se₃ had been investigated. The values of the Hall coefficient and electrical conductivity at room temperature spreads from an order of R_H11 = 1.36 × 10⁴ cm³/coul, σ₁₁ = 4.138 × 10⁻³ Ω⁻¹ cm⁻¹ and R_H = 66.55 × 10⁴ cm³/coul, σ = 0.799 × 10⁻³ Ω⁻¹ cm⁻¹ for parallel and perpendicular to c-axis, respectively. The temperature dependence of Hall mobility and carrier concentration are also studied.     

Crystal Growth and Elastic Properties of Hopeite,Zn3(PO4) · 4 H2O

Single crystals of orthorhombic Zn₃(PO₄)₃ · 4 H₂O of optical quality with dimensions up to 12 × 10 × 8 mm were grown from aqueous solutions of ZnSO₄ and NaH₂PO₄ by controlled diffusion of NH₃ into the solution. The elastic constants c_ij and the thermoelastic constants T_ij = dc_ij/dT, T temperature, were determined from ultrasonic resonance frequencies of thick plates in the range between 5 and 40 MHz and between 250 and 320 K. In respect to the longitudinal elastic stiffness hopeite behaves quasi isotropically, however, the elastic shear stiffness shows a large anisotropy of about a factor 2.5. Above 260 K the shear stiffness c₆₆ possesses a quite anomalous temperature dependence (T₆₆ > 0). Further, the linear thermal expansion reveals a strong anisotropy (α₁₁ = −3.3, α₂₂ = 3.4, α₃₃ = 33 · 10⁻⁶/K).     

Liquid-Phase Epitaxy of (Hg,Cd)Te on CdTe Substrates by a Vertical Dipping Technique

Hg_1−xCd_xTe layers on CdTe substrates were grown from Te-rich melt solutions by a vertical dipping technique using a special quasi-closed system with ground-glass sealing. Results are good reproducibilities of the electrical properties after annealing in Hg-rich atmosphere (p77 ≈ 2 · 10¹⁶ cm⁻³ μ77 ≈ 500 cm² V⁻¹ s⁻¹) and of the x-value, respectively. A horizontal position of the substrate downwards to the melt solution yields, in difference to a vertical one, to homogeneous layer thicknesses. Short meltback steps before growth leads to sharper profiles of composition.     

Kinetics of sodium fluosilicate precipitation

The formation of Na₂SiF₆ by discontinuous precipitation of dilute H₂SiF₆ with a 40% excess of an aqueous solution of NaCl under various conditions was studied. The values of induction time, number of crystals formed, their final size and their habit were determined during precipitation from solutions, whose initial supersaturation was 2 < S < 11. At S < 7–8 the crystals were formed by heterogeneous nucleation, whereas at S ≳ 7–8 homogeneous nucleation mechanism began to prevail. Once formed, the Na₂SiF₆ crystals were growing according to the screw-dislocation mechanism till they reached visible size; the corresponding values of kinetic order of nucleation and of the growth rate constant were g = 1.35 and k_g = 4.32 × 10⁻⁸ cm^2.05 sec⁻¹ g^−0.35, resp. The value of interfacial tension on the phase boundary Na₂SiF₆ crystal — saturated solution was determined (σ ∼ 52 erg/cm²). The resulting Na₂SiF₆ crystals conformed to log-normal distribution irrespective of conditions of precipitation. The dependence of the final size of crystals on supersaturation exhibited a maximum at S ∼ 6. Crystals of Na₂SiF₆ had a hexagonal habit, which was near to a spherical form at lower supersaturations, while dendritic crystals were formed at higher supersaturations.     

Plastic Deformation of Cesium Iodide Single Crystals at High Temperatures

The plastic deformation of CsI crystals of three crystallographic orientations 〈100〉. 〈110〉. and 〈111〉 at temperatures from 423 to 773 K (0.5 to 0.86T_m) and strain rates from 2 × 10⁻³ to 10⁻⁵ s⁻¹ is studied. Four-stage stres-strain curves were found, three stages being more and more distinct with an increase in temperature up to 623 K above which stage III prevails. For all the temperatures, strain rates and oreintations studied the superplasticity features (jerky flow, deformation localization, active dynamical recovery etc.) were observed. The thermal activatoin analysis has shown that the rate of high temperature deformation of CsI is controlled by dislocation climb limited in its turn by mobility of cation vacancies (quasiviscous creep).     

Ultraviolet Absorption of Hg2Cl2-and Hg2Br2 Single Crystals

The optical unpolarized absorption spectra of Hg₂Cl₂ and Hg₂Br₂ single crystals were measured in the spectral range 230–400 nm. A sharp exciton peak and other absorption bands of both halides were observed near the fundamental absorption edge. The absorption peaks due to the splitting of the halogen doublet were also observed. Positions of the exciton peaks are characteristic for the Frenkel (localized) type of excitons. Possible interpretations of the other observed bands are discussed.     

Study of optical and transport properties of K2CuCl4 · 2H2O single crystal

Optical absorption, transport properties and EPR of K₂CuCl₄ · 2H₂O single crystals have been studied. The optical absorption in UV, and visible region are characterized by a charge transfer band, and in the near infrared region at 3998, 4336, and 4480 cm⁻¹ are attributed to transitions between the stark levels of copper(II) ion in an extended octahedral crystal field. An anisotrophic ‘g’ value was observed with g_∥ = 2.12 and g_∥ = 2.24 by EPR method. The spin orbit coupling constant is found to be 500 cm₋₁. D.C. electrical conductivity measurements with temperature reveal an anisotropy characteristic of a two-dimensional layered structure and exhibit a first order irreversible structural phase-transition at 377 K, i.e. from tetragonal to monoclinic crystal system. X-ray diffraction studies and density calculations from the crystal structure data in both the phases suggest that the first order irreversible transition occurs following the loss of the two water molecules of hydration.