Reststrahlen of CdP2 single crystals at low temperatures

A dispersion analysis of reflectance spectra of CdP₂ crystals was performed and the dispersion parameters were obtained in the far infrared region (FIR) at different temperatures for the first time. Dielectric permittivity was obtained for the polarization along the a- and c-axes of a single crystal. Phonon modes are described by their oscillator parameters, i.e. the frequency, oscillator strength and the damping constant. Temperature dependence of these parameters is discussed.     

Electron density and chemical bonding in tetragonal A2B 2 5 crystals. II. ZnP2 and CdP2

The electron density of tetragonal ZnP₂ and Cdh₂ has been calculated by the pseudopotential method. The valence band of ZnP₂ and CdP₂ consists of 48 subbands grouped into 4 subbands. The Zn(Cd)–P bond proved to be ionic-covalent, with a bond charge of 0.01(2)e whose maximum is shifted toward phosphorus. The (r) maximum of the shortest P1–P3 bond lies in its middle; the bond charge values are 0.25e (ZnP₂) and 0.50e (CdP₂). The charge maximum on the P₂–P₃ bond lies near the middle of the bond; it slightly deviates from the bond direction in the (P1, P2 P3) plane, indicating anisotropy of the bond. The partial electron densities have been calculated for the four subbands of the valence band. The reason for the splitting of the phosphorus s-band into two bands in ZnP₂ and CdP₂ was found to be sp-hybridization in the region of the s-band, which is the strongest for the shortest P1–P3 bond.Kemerovo State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 5, pp. 52–56, September–October, 1993.Translated by L. Smolina     

Crystallization of ultraphosphates via the gas phase. The crystal structures of FeP4O11, ZnP4O11 and CdP4O11

The new ultraphosphates FeP₄O₁₁, ZnP₄O₁₁ and CdP₄O₁₁ of the CuP₄O₁₁ structure type were synthesized from the corresponding meta- or polyphosphates and P₄O₁₁. Crystallization via the gas phase has been achieved at elevated temperatures using a mixture of P (3 mg) and I₂ (50 mg) as mineralizer. The crystal structure consists of a two-dimensional phosphate network, built from four crystallographically independent 10-membered polyphosphate rings. Each ring contains four secondary and six tertiary PO₄-groups. Two crystallographically independent metal sites showing sixfold coordination by terminal oxygen atoms are located inbetween the phosphate layers. FeO₆-octahedra (2.028(3) Å < d̄ FeO₆ < 2.268(3) Å) and ZnO₆ octahedra (2.002(2) Å < d̄ ZnO₆ < 2.256(2) Å) exhibit slightly larger radial distortion than the CdO₆-octahedra (2.215(7) Å < d̄ CdO₆ < 2.383(3) Å).     

Mechanism of low temperature decomposition of NiO single crystals

The decomposition of NiO single crystal was investigated under dissociative conditions in the temperature interval between 330 and 850 °C in the absence of reducing gas species. An unusually fast and constant decomposition rate was measured at the lowest temperatures, coupled with an unusual largely porous microstructure of the metallic product layer. This anomalous high reaction rate was interpreted on the basis of a decomposition mechanism implying the dissociative vaporization of the oxide followed by the condensation of the metal. The proposed mechanism is supported by the microstructure of the product and of the reacting interface. The complex dependence of reaction rate from temperature was shown to be related to a collapse of the porous product to form a compact metal layer at higher temperatures due to sintering.     

Mixed-crystal infrared studies of chain folding in polyethylene single crystals: Effect of crystallization temperature

Mixed crystals of polyethylene (PEH) and various-molecular-weight perdeuterated polyethylenes (PEDs) have been prepared at 80°C and their infrared spectra compared with those of samples grown at 55°C. Concentrations of 80 PEH/1 PED were required in the former case to eliminate segregation effects whereas 40 PEH/1 PED sufficed in the latter. Resolution of the observed CD₂ bend contour was most reasonably achieved with a crystalline singlet and two crystalline doublets, in addition to a contribution (ca. 15%) from the noncrystalline component. The singlet, comprising about 20% of the crystalline area, contains contributions from both isolated stems and (200) adjacent reentry folding. Random reentry folding is therefore not a predominant mode of chain organization in polyethylene single crystals. The inner of the two doublets arises from adjacent reentry folding along single (110) planes, and is present for all PED molecular weights. For low-molecular-weight fractions this splitting is consistent with the number of stems of one PED molecule allowed in the crystal. The outer doublet arises from multiple (110) plane adjacency, and is present for intermediate and high molecular weights. An analysis of both doublets suggests that at high molecular weights a single molecule can crystallize with noncontiguous regions of adjacent stem domains.     

Q-band EPR and ENDOR of low temperature X-irradiated beta-D-fructose single crystals

Beta-D-fructose single crystals were in situ X-irradiated at 80 K and measured using electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR) and ENDOR-induced EPR (EIE) techniques at Q-band (34 GHz) microwave frequencies. The measurements revealed the presence of at least four carbon-centered radicals stable at 80 K. By means of ENDOR angular variations in the three principal crystallographic planes, six proton hyperfine coupling tensors could be determined and were assigned to four different radicals by the aid of EIE. Two of the radicals exhibit only beta-proton hyperfine couplings and reveal almost identical EIE spectra. For the other two radicals, the major hyperfine splitting originates from a single alpha-proton hyperfine coupling and their EIE spectra were also quite similar. The similarity of the EIE spectra and hyperfine tensors led to the assumption that there are only two essentially different radical structures. The radical exhibiting only beta-proton hyperfine couplings was assigned to a C3 centered radical arising from H3 abstraction and the other radical suggested to be an open-ring species with a disrupted C2-C3 bond and a double C2-O2 bond. A possible formation mechanism for the latter open-ring radical is presented. By means of cluster density functional theory (DFT) calculations, the structures of the two radicals were determined and a fairly good agreement between the calculated and experimental hyperfine tensors was found.     

Influence of gas atmosphere and temperature on the conductivity and the photoconductivity of a TiO2 single crystal in the surface region

The electrical photoconductivity and conductivity at (and near) the surface of a TiO(2) single crystal (rutile) was studied in a range of temperatures between 300 and 573 K and under different ambient gases (oxygen and nitrogen) by means of impedance spectroscopy. The long times required (many hours) to reach steady state photoconductivity can be explained by the reduction of the material upon illumination. At about 475 K a maximum is observed in the equilibrium photoconductivity and a minimum in the rate constants of the rise and decay after switching on and off, respectively, the light. After switching off the light a fast decay takes place during the first milliseconds followed by a slow exponential decay. The first one is related to recombination through defects, while the latter is due to re-oxidation processes of the material. The results are correlated with measurements of photocatalytic activity.     

Photoelectrical properties of TlGaSe2 single crystals

The spectral distribution of photocurrent (PC) of TlGaSe₂ single crystals in the range of wavelengths between 500 nm and 700 nm possesses a single maximum at 2.04 eV corresponds to the direct energy band gap of this crystal. The PC is enhanced dramatically by pre-illuminations at low temperatures with band gap light. The temperature dependence of PC of the sample investigated in the temperature range from 80 K to 300 K at constant heating rate shows that the overlapping peaks in the PC spectrum are direct reflection of the Thermally Stimulated Current (TSC) associated with the several trapping levels. The PC response is strongly dependent on the degree of occupancy of traps. The wavelength at the maximum of the PC spectrum is found to be dependent on the wavelength scan direction being up or down. The ferroelectric phase transitions of TlGaSe₂ are detected at ∼108 K and ∼118 K in the PC spectrum.     

单斜ZnP2负极材料的锂化机理及性能

过渡金属磷化物电位低且比容量高, 是有发展前景的锂离子电池(LIBs)负极材料. 其中, ZnP₂属于双活性负极材料, Zn与P都能与Li⁺发生反应, 储Li⁺性能更具有竞争力. 但是, 对于ZnP₂的锂化机理及产物尚不明确. 采用第一性原理计算和电化学测试方法研究了ZnP₂的电子性质和电化学性能, 通过理论计算和实验测试相结合阐述了ZnP₂的锂化机制. 首先, 以密度泛函理论(DFT)计算揭示了ZnP₂的锂化机理、Li⁺扩散路径、势垒和理论比容量(1477 mAh/g). 其次, 通过直流电弧等离子体法及固相烧结法合成ZnP₂, 并测试其首圈放电曲线, 显示放电容量为1439 mAh/g, 与理论计算结果相近. 此外, 薄膜X射线衍射(XRD)检测最终产物成分为LiZn和Li₃P, 与DFT计算结果一致.     

The synthesis of ZnP4 based on liquid–solid reaction under high pressure and temperature

In this article we reported the successful high pressure and temperature synthesis of micron-sized zinc tetraphosphide (ZnP₄) crystals based on the liquid–solid reaction between Zn and P at a large-volume cubic press. Techniques of X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray analysis (EDXA) were employed to investigate the phase structure, grain size, morphology and stoichiometric ratio of crystals. The results indicate that the synthesized ZnP₄ has a tetragonal structure with the space group of P41212, and the grains with size of about 50 μm can be prepared at 4.0 GPa and 1000 °C. We also obtained the pressure–temperature (P–T) formation region of ZnP₄ and discussed the formative mechanism of ZnP₄ crystals.     

Effect of doping an organic molecule ligand on TGS single crystals

Good quality single crystals of thiourea-doped triglycinesulphate (TuTGS) a new semiorganic nonlinear optical (NLO) crystal has been successfully grown from aqueous solution by slow evaporation method. The solubilities under various solvents in different proportions have been studied. The structural characterization of the grown crystals was carried out by X-ray diffraction. The grown crystals were subjected to FTIR and Raman analyses for vibrational assignments. The optical absorption coefficient alpha was analysed and interpreted to be allowed in the direct transition. The values of allowed direct energy gap (Eg) for undoped and doped crystals were calculated. It was found that Eg values were decreased with organic molecule doping. The powder technique of Kurtz and Perry confirm the NLO property of the grown crystal.     

Millimetre-wave studies on single crystals of the organic radical 2-benzimidazolyl nitronyl nitroxide

We report temperature dependent millimetre-wave spectroscopic experiments on single crystals of the organic molecular magnet 2-benzimidazolyl nitronyl nitroxide, in the range 1.4–100 K. This organic radical shows quasi one-dimensional (1-d) ferromagnetic intermolecular interactions with the intrachain exchange coupling constant J/k_B = +22 K and interchain coupling constant J′/k_B = 0.24 K. The linewidth of the electron spin resonance at low temperatures was seen to be considerably broadened as compared to that at higher temperatures. This is consistent with the low dimensional behaviour of the linewidth predicted theoretically. We also see a shift in resonance field at low temperatures. We also present the results of angular dependence experiments carried out at temperatures of 1.4 and 50 K, and frequency dependence experiments at 1.4 and 50 K.     

Preparation and characterization of several II-IV-V2 chalcopyrite single crystals

Single crystals of ZnSiP₂, ZnGeP₂, ZnGeP_1.8As_0.2, and ZnGeP_1.6As_0.4 have been grown by several techniques and their electronic and optical properties were compared. For ZnSiP₂ there are marked absorption bands at 10 and 11.5 μm, and at 13 μm for ZnGeP₂. Upon substitution of 10 mole% of arsenic for phosphorus, the latter band does not shift to higher wavelengths. Further substitution of arsenic for phosphorus in ZnGeP₂ showed a weak second band at 9.8 μm.     

Optical properties of anthracene single crystals in the excitonic region of the spectrum between 4 and 10.5 eV

The optical constants in the photon energy range between 4 and 10.5 eV for E ?b on (001) and E ?L and E ⊥ _L on the (010) plane are discussed. In particular the influence of macroscopic fields on the optical properties of anisotropic crystals is considered. For _E ? a on the (001) plane reflection spectra have been measured at various angles of incidence. These data and results obtained recently by Hymowitz and Clark for several artificially prepared crystal faces are discussed on the basis of the frequency dependend dielectric functions. New information on the directional dispersion of exciton bands is thus obtained.     

Dielectrophoretic assembly of grain-boundary-free 2D colloidal single crystals

Dielectrophoresis (DEP) force-assisted assembly of a colloidal single photonic-crystal monolayer in a microfluidic chamber was demonstrated. Negative DEP force with a high-frequency AC electric field induced the compression of colloidal microspheres to form a colloidal crystal domain at the center of a hexapolar-shaped electrode. While typical assembly by monotonic DEP force forms multicrystalline domains containing crystal defects, repetitions of the DEP/relaxation cycle significantly facilitated crystal growth of 10μm monodispersed polystyrene microspheres, allowing a grain-boundary-free single-crystal monolayer domain of ca. 200μm in size. Microsphere size as well as size distribution affected the formation of the single-crystal domain. A simple method was used to immobilize the single-crystal domain on the glass substrate without losing its crystallinity.     

Influence of Zn2+ ion on the organometallic l-alanine cadmium chloride single crystals

The single crystals of pure and zinc chloride-doped l-alanine cadmium chloride (LACC), an organometallic nonlinear optical material, are grown by a slow evaporation technique. The grown crystals were subjected to X-ray diffraction analysis, scanning electron microscopic study, and energy-dispersive analysis by X-ray and thermal studies. The second harmonic generation was confirmed by the Kurtz and Perry powder technique. The dielectric measurements were carried out for different frequencies at different temperatures. The second harmonic efficiency and dielectric constant increases significantly due to introduction of smaller ionic radii Zn²⁺ ion into the lattice of pure LACC crystal; so that the zinc chloride-doped LACC crystals are found to be potential material for nonlinear frequency conversion.     

Effect of chain defects on the morphology and thermal behavior of solution-grown single crystals of syndiotactic polypropylene

The morphology of solution-grown single crystals of syndiotactic polypropylene with different degree of stereoregularity is compared. A sector formation phenomenon, found in some monolayer single crystals, is discussed in terms of possible crystallographic fold planes, growth planes, and gemination planes. A correlation between thermodynamic and morphological properties such as apparent enthalpy of fusion, critical long spacing, critical annealing temperature, and the number of configurational chain defects along the macromolecule has been found. Two endothermic peaks are observed in the DSC thermograms of single-crystal aggregates of syndiotactic polypropylene. The low-temperature peak is attributed to melting of crystals or parts of crystals with incorporated chain defects. The high-temperature peak corresponds to the melting endotherm of more regular crystalline zones. The peak-area ratio seems to depend on the degree of stereoregularity.     

Fluorescence reabsorption in anthracene single crystals: Lifetime variations with emission wavelength and temperature

Fluorescence spectra and lifetimes of anthracene melt-grown single crystals and sublimation flakes have been examined at 298 and 77°K, using a mono-photon counting technique for the lifetime measurements. The observed emission decay times were nearly independent of the excitation wavelength, though a small dependence of the fluorescence spectrum on the excitation wavelength was noted. By contrast, large variations of fluorescence lifetimes in thick crystals were found as a function of emission wavelength. For thick melt-grown single crystals at 298°K the lifetime was found to increase from 9.8 nsec at 405 nm to 20.4 nsec at 445 nm. For sublimation flakes at 77°K and at 298°K and for thick melt-grown crystals at 77°K, the lifetimes were less than 10 nsec and were nearly independent of emission wavelength. Despite these relatively large variations in lifetimes, the decay rates at each separate wavelength remained exponential, within experimental error. Theoretical calculations were made of emission lifetimes based on a model with one reabsorbing state. The calculations are in substantial agreement with the experimental results.     

Bromine enrichment in the near-surface region of Br-doped NaCl single crystals diagnosed by Rutherford backscattering spectrometry

Bromine released from sea-salt aerosols and seawater ice is known for its high chemical reactivity. Previous studies have suggested that its availability to the gas-phase could be enhanced by segregation processes increasing Br concentration on the aerosol surface as compared to the bulk. However, little is known about the composition within the near-surface region, that is, the outermost approximately 100 monolayers. We used Rutherford backscattering spectrometry (RBS) to measure Br concentration profiles to a depth of about 750 nm of Br-doped NaCl single crystals to characterize the thermodynamics and kinetics of Br segregation to the near-surface region in moist air. These experiments were carried out on cleavage planes of melt-grown and of annealed solution-grown crystals at room temperature and relative humidities (RH) too low for formation of a stable liquid phase. Segregation of Br was below the detection limit on melt-grown crystals with Br/Cl = 0.01. In the case of annealed solution-grown crystals with Br/Cl = 0.002, average segregations of (0.24 +/- 0.11) x 10(15) and (0.42 +/- 0.12) x 10(15) Br atoms cm-2 were observed at 50% and 65% RH, respectively. No segregation was found at 20% RH. The observed Br segregation can be explained by the formation of an adsorbed liquid layer (depending on crystal surface properties and relative humidity) and preferential, diffusion-limited dissolution of Br into this layer according to the partition coefficient of Br between aqueous and solid NaCl. The thickness of the adsorbed liquid layer, which depends on crystal surface geometry and on relative humidity, can be estimated to range from 4 to at most 59 nm on the basis of measured Br concentrations and partition coefficients. Applying this concept of partitioning to natural sea salt suggests a Br/Cl molar ratio of up to 0.2 in adsorbed surface water of crystallized natural aerosol particles compared to about 0.0015 in seawater. This would have a major impact on heterogeneous reactions on sea-salt particles under dry conditions such as in the freeze-dried Arctic boundary layer.     

Synthesis,structural characterization,and electronic structure of the novel Zintl phase Ba2ZnP2

The novel Zintl phase dibarium zinc diphosphide (Ba₂ZnP₂) was synthesized for the first time. This was accomplished using the Pb flux technique, which allowed for the growth of crystals of adequate size for structural determination via single‐crystal X‐ray diffraction methods. The Ba₂ZnP₂ compound was determined to crystallize in a body‐centered orthorhombic space group, Ibam (No. 72). Formally, this crystallographic arrangement belongs to the K₂SiP₂ structure type. Therefore, the structure can be best described as infinite [ZnP₂]^4? polyanionic chains with divalent Ba²⁺ cations located between the chains. All valence electrons are partitioned, which conforms to the Zintl–Klemm concept and suggests that Ba₂ZnP₂ is a valence‐precise composition. The electronic band structure of this new compound, computed with the aid of the TB–LMTO–ASA code, shows that Ba₂ZnP₂ is an intrinsic semiconductor with a band gap of ca 0.6 eV.