EPR and optical absorption studies of Cu<Superscript>2+</Superscript> ions in [ZnPd(CN)<Subscript>4</Subscript>(C<Subscript>4</Subscript>H<Subscript>12</Subscript>N<Subscript>2</Subscript>O<Subscript>2</Subscript>)] single crystals

A Cu²⁺-doped single crystal of catena-trans-bis(N-(2-hydroxyethyl)-ethylenediamine) zinc(II)-tetra-m-cyanopaladate(II) [ZnPd(CN)₄(C₄H₁₂N₂O₂)] complex has been investigated by electron paramagnetic resonance (EPR) technique at room temperature. EPR spectra indicate that Cu²⁺ ions substitute for magnetically equivalent Zn²⁺ ions and form octahedral complexes in [ZnPd(CN)₄(C₄H₁₂N₂O₂)] hosts. The crystal field affecting the Cu²⁺ ion is nearly axial. The optical absorption studies show two bands at 322 nm (30864 cm⁻¹) and 634 nm (15337 cm⁻¹) which confirm the axial symmetry. The spin Hamiltonian parameters and the relevant wave function are determined.     

Vibrational spectra of monoisotopic SiH<Subscript>4</Subscript> and GeH<Subscript>4</Subscript> in low-temperature matrices

IR absorption spectra of monoisotopic ²⁸SiH₄ and ⁷⁶GeH₄ are studied in Ar and N₂ matrices at 10 K. It is shown that the absorption spectra of silane and germane are similar in the regions of the stretching ν₃ and bending ν₄ vibrations. Four groups of bands can be separated out in the spectra of each molecule: (1) narrow bands characteristic of the matrix isolation studies, (2) broad bands, (3) diffuse absorption with a large value of the spectral moment M ₂^* the intensity of which increases upon annealing, and (4) bands of dimers the intensity of which increases quadratically with concentration. The spectra of ²⁸SiH₄ and ⁷⁶GeH₄ in nitrogen matrices contain a triplet in the stretching region and a doublet in the bending region, which is explained by the change in the molecular symmetry from T _d to C _3V on passage from the gas phase to solid nitrogen.     

Check of the scaling procedure of track structures of ionizing radiation in nanometric volumes

In nanodosimetry, the track structure of ionizing radiation is characterized by the probability distribution of the number of ionizations produced by an ionizing particle in a target volume. By Monte-Carlo simulations of the track structure, this so called ionization cluster size distribution can be determined for nanometric cylindrical water targets used as substitute for the radiation sensitive biological target, namely a DNA-segment of about 20 base pairs length. Measurements of ionization cluster size distributions are carried out in an ion-counting nanodosimeter filled with an appropriate working gas at low pressure. A scaling procedure was proposed by Grosswendt (2006) to derive an operating pressure depending on the working gas for which the measured ionization cluster size distribution becomes equivalent to the ionization cluster size distribution within a nanometric target of liquid water. This scaling procedure was previously tested by means of Monte-Carlo simulations and is now tested experimentally.Ionization cluster size distributions produced by mono-energetic proton and alpha particle beams in the energy range between 0.1 MeV and 20 MeV were measured at the accelerator facilities of the PTB. The working gases used in this experiment were C₃H₈ and N₂. According to the NIST databases for stopping power and mean ionization energy (NIST, 2009), equivalent cluster size distributions for protons and alpha particles should be obtained for pressures of 0.25 mbar C₃H₈ and 1.2 mbar N₂. Measurements reveal the best agreement with pressures of 0.425 mbar C₃H₈ and 1.2 mbar N₂ for protons and 0.46 mbar C₃H₈ and 1.2 mbar N₂ for alpha particles.     

Emission of cyan upon excitation of nitrogen,air, and N<Subscript>2</Subscript>-CH<Subscript>4</Subscript> mixture by discharge pulses in an inhomogeneous electric field

We have studied spectral and amplitude-time characteristics of the emission by nitrogen, air, and the N₂-CH₄ mixture upon excitation by nanosecond and microsecond high-voltage discharge pulses in an inhomogeneous electric field in the pressure range of 0.01–3 atm. In the pulsed and pulse-periodic discharge regimes, we have observed emission bands of the violet system of cyan, the transition B ²Σ⁺ → X ²Σ⁺, which were comparable in intensity with bands of the (2⁺) system of nitrogen. We show that, in the pulsed regime, the highest intensity of the violet system of cyan is observed in the N₂-CH₄ mixture. We show that, in the pulse-periodic discharge in nitrogen with a small amount of a carbon-containing admixture, upon contracting the discharge, the efficiencies of formation and emission of the violet system of cyan considerably increase. We confirm that admixtures of oxygen to nitrogen lead to suppression of the emission of the violet system of cyan molecules.     

Synthesis and characterization of electron beam evaporated LiCoO<Subscript>2</Subscript> thin films

LiCoO₂ thin films were prepared by electron beam evaporation technique using LiCoO₂ target with Li/Co ratio 1.1 in an oxygen partial pressure of 5 × 10⁻⁴ mbar. The films prepared at substrate temperature T _s < 573 K were amorphous in nature, and the films prepared at T _s > 573 K exhibited well defined (104), (101), and (003) peaks among which the (104) orientation predominates. The X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) data revealed that the films prepared in the substrate temperature range 673–773 K are nearly stoichiometric. The grain size increases with an increase of substrate temperature. The Co–e_g absorption bands, are empty and their peak position lies at around 1.7 eV above the top to the Co–t_2g bands. The fundamental absorption edge was observed at 2.32 eV. The films annealed at 1,023 K in a controlled oxygen environment exhibit (104) out plane texture with large grains. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006     

Effect of high pressure on the crystal and magnetic structures of La<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>CoO<Subscript>3</Subscript> cobaltite

The atomic and magnetic structures of La_0.5Ca_0.5CoO₃ cobaltite have been studied by the neutron diffraction technique at high pressures of up to 4 GPa in the 10- to 300-K temperature range. The pressure dependences of the structural parameters have been obtained. The Curie temperature increases with the pressure with the coefficient dT _C/dP = 1 K/GPa, demonstrating the stability of the ground ferromagnetic (FM) state. The pressure dependence of the ground FM state in La_0.5Ca_0.5CoO₃ is in drastic contrast with that for La_{1 − x} Ca _x CoO₃ at a lower calcium content (x < 0.3). For the latter compound, the pressure suppressed the ground FM state and a large negative pressure coefficient of the Curie temperature (dT _C/dP ∼ −10 K/GPa) was observed. The nature of such a phenomenon is analyzed in the framework of the double exchange model also taking into account the changes in the electron configuration of Co³⁺ ions.     

The effect of temperature and pressure on the heat conductivity of TlSbC<Stack><Subscript>2</Subscript><Superscript>VI</Superscript></Stack> (<Emphasis Type="Italic">C</Emphasis><Superscript>VI</Superscript> → S,Se, Te)

The effect of temperature and pressure on heat conductivity of ternary compounds TiSbC ₂^VI (C ^VI → S, Se, Te) in the solid and liquid states in a temperature range of 300–800 K, as well as under the pressure up to 0.35 GPa in a temperature range of 275–450 K, is studied. The dependence of heat conductivity on average atomic weight under the S → Se → Te transition is found. Analysis of the experimental data makes it possible to attribute TlSbS₂ to the class of substances exhibiting semiconductor-semiconductor melting behavior.     

Einstein<Emphasis Type="Italic">A</Emphasis>-coefficients for rotational transitions in the ring-chain isomer of C<Subscript>5</Subscript>H<Subscript>2</Subscript>

Laboratory formation of four isomers of C⁵H² molecule is reported and detection of the ring-chain isomer (isomer 1) of C₅H₂ in cosmic objects has been suggested. For identification of a molecule in cosmic objects, one of the required input data is EinsteinA-coefficients (radiative transition probabilities) for the molecule. Here, we report EinsteinA-coefficients for electric dipole transitions in the ring-chain isomer of C₅H₂ among the rotational levels of the ground electronic and ground vibrational states up to 21 cm⁻¹.     

Material ablation and plasma state for single and collinear double pulses interacting with iron samples at ambient gas pressures below 1 bar

The influence of the ambient gas pressure on ablated material and the plasma state of laser-inducedplasmas using single and collinear double pulses is studied. A Q-switchedNd:YAG laser pulse is focused on iron samples in air at pressures ranging from 0.1 to 1013 mbar. At 1013 mbar double pulses ablate up to a factor of 4.6 more material than single pulses of the same energy. Whereas between 1013 mbar and 100 mbar a strong variation of the ablation ratio is found, the pressure dependence vanishes below 100 mbar. Electron densities in the plasma are always higher for single pulses and increase monotonously with higher ambient pressures. While the electron density for single and double pulses at 1013 mbar is close to the same value of about 10¹⁷ cm^-3, the electron temperature is more than 1500 K higher for double pulses. The plasma state achieved with double pulses at atmospheric pressure is similar to that obtained with single pulses of the same energy at a pressure of 100 mbar. Thus the effect of double pulses can be interpreted as a “laser-generated vacuum” in terms of the formation of a transient localized low particle density region in the interaction region. PACS 52.38.Mf; 78.47.+p; 42.62.Fi     

Structural and magnetic phase transitions in Pr<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> at high pressures

The crystal structure and Raman spectra of Pr_0.7Ca_0.3MnO₃ manganite at high pressures of up to 30 GPa and the magnetic structure at pressures of up to 1 GPa have been studied. A structural phase transition from the orthorhombic phase of the Pnma symmetry to the high-pressure orthorhombic phase of the Imma symmetry has been observed at P ∼ 15 GPa and room temperature. Anomalies of the pressure dependences of the bending and stretching vibrational modes have been observed in the region of the phase transition. A magnetic phase transition from the initial ferromagnetic ground state (T _C = 120 K) to the A-type antiferromagnetic state (T _N = 140 K) takes place at a relatively low pressure of P = 1 GPa in the low-temperature region. The structural mechanisms of the change of the character of the magnetic ordering have been discussed.     

Geometries and electronic structures of Ga<Subscript>2</Subscript>Se<Subscript>3</Subscript>, Ga<Subscript>3</Subscript>Se<Subscript>2</Subscript> and their anions. Theoretical insights

We hereby report a theoretical study on the equilibrium geometries, electronic structures and harmonic vibrational frequencies of Ga₂Se₃, Ga₃Se₂ and their anions. The ground and low-lying excited states of Ga₂Se₃⁻, Ga₂Se₃, Ga₃Se₂⁻ and Ga₃Se₂ are studied at the B3LYP and/or MP2 and CCSD(T) levels in conjunction with 6-311+G(d) and 6-311+G(2df) one particle basis sets. Ga₂Se₂⁻ adopts the C_2v kite geometry while Ga₂Se₃ has a ‘V’ geometry. Ga₃Se₂⁻ has a three-dimensional ‘D_3h ’ geometry and Ga₃Se₂ prefers the three-dimensional ‘C_2v ’ structure. Electron detachment energies from the ground electronic states of the anions to several neutral states are reported and discussed. At CCSD(T)//MP2 level, the adiabatic electron affinity (AEA) of Ga₂Se₃ is calculated to be 3.23 eV when using the 6-311+G(2df) basis set and that of Ga₃Se₂ is 2.77 eV with the 6-311+G(d) basis set. The findings of this research are analyzed and compared with gallium oxide and sulfide analogues.     

The structure of fullerite C<Subscript>60</Subscript> intercalated with molecular oxygen

A (O₂) _x C₆₀ sample with a high content of oxygen (x ≥ 0.4) and free of technological solvent impurities was obtained by precipitation from solution. For the first time, the results of the determination of the x coefficients using ¹³C NMR and elemental analysis were compared. It was shown by Raman spectroscopy, mass spectrometry, and NMR that the inclusion of oxygen into fullerite was accompanied by a decrease in the frequency of O=O stretching vibrations by no less than 12 cm⁻¹ compared with gaseous O₂. Nevertheless, oxygen exists in the molecular form in (O₂)_0.4C₆₀ and is released in the form of O₂ as the sample is heated to 373 K. The number of oxygen molecules occupying octahedral pores closets to the fullerene molecule takes on all the possible values, from 0 to 6. At room temperature, the (O₂) _x C₆₀ sample lost oxygen much more slowly than similar products prepared by diffusion saturation of pure fullerite with oxygen.     

Magnetic properties of nanoparticle La<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> under applied hydrostatic pressure

Pressure effects on magnetic properties of two La_0.7Ca_0.3MnO₃ nanoparticle samples with different mean particle sizes were investigated. Both the samples were prepared by the glycine-nitrate method: sample S—as-prepared (10 nm), and sample S₉₀₀—subsequently annealed at 900 °C for 2 h (50 nm). Magnetization measurements revealed remarkable differences in magnetic properties with the applied pressure up to 0.75 GPa: (i) for S sample, both transition temperatures, para-to-ferromagnetic T _C = 120 K and spin-glass-like transition T _f = 102 K, decrease with the pressure with the respective pressure coefficients dT _C/dP = −2.9 K/GPa and dT _f/dP = −4.4 K/GPa; (ii) for S₉₀₀ sample, para-to-ferromagnetic transition temperature T _C = 261 K increases with pressure with the pressure coefficient dT _C/dP = 14.8 K/GPa. At the same time, saturation magnetization M _S recorded at 10 K decreases/increases with pressure for S/S₉₀₀ sample, respectively. Explanation of these unusual pressure effects on the magnetism of sample S is proposed within the scenario of the combined contributions of two types of disorders present in the system: surface disorder introduced by the particle shell, and structural disorder of the particle core caused by the prominent Jahn–Teller distortion. Both disorders tend to vanish with the annealing of the system (i.e., with the nanoparticle growth), and so the behavior of the sample S₉₀₀ is similar to that previously observed for the bulk counterpart.     

C<Subscript>60</Subscript> fullerene as an η<Superscript>6</Superscript> ligand in π complexes of transition metals

The possible existence of complexes formed by the C₆₀ fullerene or its derivatives with transition metals interacting with the carbon cage via η⁶−π type bonding is discussed. The derivatives C₆₀ R ₆ of the C₆₀ fullerene (R = −, H, F, Cl, Br, CN) are analyzed using the density functional method within the Perdew-Burke-Ernzerhof approximation. In these molecules, the R groups are attached to carbon atoms located in the α positions with respect to the common hexagon of the C₆₀ fullerene. The structure and electron configuration of complexes formed by these molecules with Cr(C₆H₆), Cr(CO)₃, MoC₆H₆, and Mo(CO)₃ particles are modeled. The “dimer” systems C₆₀R₆-M-R ₆C₆₀ (M = Cr, Mo, R =-, H, F) are investigated in which two fullerene molecules interact via a transition-metal atom. It is found that the introduction of six R groups in the α sites with respect to the common hexagon of C₆₀ favors the formation of complexes of these derivatives of the C₆₀ fullerene with the Cr(C₆H₆), Cr(CO), Mo(C₆H₆), and Mo(CO)₃ particles in which η⁶-π type bonds arise between the metal and the atoms of the hexagon fringed with the R groups. It is also demonstrated that analogous complexes with a “bare” C₆₀ fullerene are possible, but they are significantly less stable. The (C₆H₆) M-R ₆C₆₀ R ₆-M (C₆H₆) complexes of particles M(C₆H₆) (M= Cr, Mo) and derivatives R ₆C₆₀ R ₆ (R =-, H, F, Cl, Br) are studied. In the R ₆C₆₀ R ₆ molecule, six R groups are located in the α sites with respect to the common hexagon of the C₆₀ fullerene and six other groups fringe the opposite hexagon. The obtained results can be applied to planning synthesis of new complexes that C₆₀ fullerene derivatives can form with transition metals. Original Russian Text ￠ E.G. Gal’pern, A.R. Sabirov, I.V. Stankevich, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 12, pp. 2220–2223.     

Comparative Plasma Chemical Reaction Studies of CH4/Ar and C2Hm/Ar (m = 2,4,6) Gas Mixtures in a Dielectric Barrier Discharge

Plasma chemical reactions in CH4/Ar and C₂H_m/Ar (m = 2, 4, 6) gas mixtures in a dielectric barrier discharge at medium pressure (300 mbar) have been investigated. From mass spectrometry the production of H₂ and formation of larger hydrocarbons such as C_nH_m with up to n = 12 is inferred. Hydrogen release is most pronounced for CH₄ and C₂H₆ gas mixtures. Fourier Transform InfraRed (FTIR) spectroscopy reveals the formation of substituted alkane (sp³), alkene (sp²), and alkyne (sp) groups from the individual gases which are used in this work. Abundant formation of acetylene occurs from C₂H₄ and to a lesser extent from C₂H₆ and CH₄ precursor gases. The main reaction pathway of acetylene leads to the formation of large molecules via C₄H₂ and, eventually, to nano‐size particles. The experimental results are in reasonable agreement with simulations which predict a pronounced electron temperature and gas pressure dependency. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and magnetic phase transitions in Pr<Subscript>0.15</Subscript>Sr<Subscript>0.85</Subscript>MnO<Subscript>3</Subscript> at high pressure

The crystal and magnetic structures of Pr_0.15Sr_0.85MnO₃ manganite have been studied by means of powder X-ray and neutron diffraction in the temperature range 10–400 K at high external pressures up to 55 and 4 GPa, respectively. A structural phase transition from cubic to tetragonal phase upon compression was observed, with large positive pressure coefficient of transition temperature dT _ct /dP = 28(2) K/GPa. The C-type antiferromagnetic (AFM) ground state is formed below T _N ≈ 260 K at ambient pressure. While at ambient pressure the structural and magnetic transition temperatures are close, T _ct ~ T _N , upon compression they become decoupled with T _N ≪ T _ct due to much weaker T _N pressure dependence with coefficient dT _N /dP = 3.8(1) K/GPa.     

Electrical characterization of the [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>][N(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>]ZnCl<Subscript>4</Subscript> compound

The [N(CH₃)₄][N(C₂H₅)₄]ZnCl₄ compound has been synthesized by a solution-based chemical method. The X-ray diffraction study at room temperature revealed an orthorhombic system with P2₁2₁2 space group. The complex impedance has been investigated in the temperature and frequency ranges 420–520 K and 200 Hz–5 MHz, respectively. The grain interior and grain boundary contribution to the electrical response in the material have been identified. Dielectric data were analyzed using the complex electrical modulus M ^* for the sample at various temperature. The modulus plots can be characterized by full width at half height or in terms of a non-exponential decay function ϕ(t) = exp[(−t/τ) ^β ]. The detailed conductivity study indicated that the electrical conduction in the material is a thermally activated process. The variation of the AC conductivity with frequency at different temperatures obeys the Almond and West universal law.     

Concentration of Cr<Superscript>4+</Superscript> impurity ions and color centers as an indicator of saturation of forsterite crystals Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> with oxygen

The influence of the oxygen partial pressure P _{O 2} in the growth atmosphere on the coefficient of chromium distribution between the crystal and the melt of forsterite, the Cr³⁺ and Cr⁴⁺ ion contents in crystals, and the concentration of color centers induced by irradiation has been investigated. It has been established that the crystals grown at low oxygen partial pressures P _{O 2} (0.01–0.05 kPa) are characterized by low concentrations of Cr⁴⁺ ions and color centers. A change in the oxygen partial pressure to P _{O 2} ∼ 0.85 kPa leads to an increase in the Cr⁴⁺ center concentration by a factor of ∼10 and in the color center concentration by a factor of ∼5. A further increase in the oxygen partial pressure to P _{O 2} to 12 kPa remains the concentration of these centers almost unchanged. A model has been proposed according to which the intrinsic defects formed under conditions of a relative excess of oxygen leads to both the self-oxidation of chromium and the formation of color centers in the forsterite crystals under irradiation.     

Possible manifestation of spin fluctuations in the temperature behavior of the resistivity of Sm<Subscript>1.85</Subscript>Ce<Subscript>0.15</Subscript>CuO<Subscript>4</Subscript> thin films

A pronounced step-like (kink) behavior in the temperature dependence of resistivity ρ(T) is observed in the optimally doped Sm_1.85Ce_0.15CuO₄ thin films around T _sf = 87 K and attributed to the manifestation of strong-spin fluctuations induced by Sm³⁺ moments with the energy ħω_sf = k _B T _sf ≃ 7 meV. The experimental data are found to be well fitted by the residual (zero-temperature) ρ_res, electron-phonon ρ_e-ph(T) = AT, and electron-electron ρ_e-e(T) = BT ² contributions in addition to the fluctuation-induced contribution ρ_sf(T) due to thermal broadening effects (of the width ω_sf). According to the best fit, the plasmon frequency, impurity scattering rate, electron-phonon coupling constant, and Fermi energy are estimated as ω_p = 2.1 meV, τ ₀ ⁻¹ = 9.5 × 10⁻¹⁴ s⁻¹, λ = 1.2, and E _F = 0.2 eV, respectively. The text was submitted by the authors in English.     

Long- and short-range order in the Pd<Subscript>6</Subscript>B monoclinic superstructure and M<Subscript>6</Subscript>X<Subscript>5</Subscript> and M<Subscript>6</Subscript>X allied superstructures

Symmetry analysis of the Pd₆B monoclinic superstructure (space group C2/c) formed in the cubic (with the B1 structure) solid solution of boron in palladium (PdB _y ) has been carried out. The formation of this superstructure proceeds as a first-order phase transition via the disorder-order channel including nine nonequivalent superstructure vectors of four stars {k ₁₀}, {k ₄}, {k ₃}, and {k ₀}. For the Pd₆B monoclinic super-structure (space group C2/c), the distribution function for boron atoms is calculated and the interval of admissible values of the long-range order parameters is defined. It is shown that the transition channel determined in this way coincides with the channel in which the M₆X monoclinic superstructure (space group C2) is formed; therefore, the Pd₆B superstructure can also be described in space group C2 to the same degree of accuracy. The higher symmetry of the monoclinic model (space group C2/c) suggests that it describes the structure of the Pd₆B phase (Pd₆B□₅), as well as of mutually inverse phases M₆X□₅ and M₆X₅□, more adequately than the model with space group C2. It is shown that superstructures of the M₆X□₅ type (space groups C2/c, C2, C2/m, and P3₁) and inverse superstructures of the M₆X₅□ type with the same space groups have the positions of the nearest surrounding of metal atoms by two types of nonmetallic sublattice sites located in the first and second coordination spheres.