Structural, spectroscopic and crystal field analyses of Ni2+ and?Co2+ doped Zn2SiO4 powders

In this paper we presented structural and spectroscopic study of zinc silicate powder samples doped with divalent nickel and cobalt ions. Results of the Rietveld structural refinement, combined with optical spectroscopic study and theoretical crystal field calculations, are presented and discussed. X-ray diffraction studies were performed to establish reliable structure of the doped samples; in this way the interionic distances and chemical bond angles in Zn₂SiO₄:Co²⁺ and Zn₂SiO₄:Ni²⁺ were calculated and are reported for the first time. The room temperature reflection spectra of the prepared samples were measured in a spectral region from 4000 to 50000 cm^?1. The exchange charge model of crystal field has been applied to analyze the experimental spectra and assign all observed details in the spectra to the corresponding electronic transitions between the Co²⁺ and Ni²⁺ crystal field energy levels. The only input information for the model calculation was the experimentally obtained structural data, which were used for the calculations of the crystal field parameters with subsequent diagonalization of the crystal field Hamiltonian for both ions. Agreement between the calculated and experimentally detected energy levels of impurity ions was good. On the basis of the crystallographic and crystal field studies it was established that there exists a systematic trend of preferential occupation of one out of two possible crystallographic sites (namely, Zn2) for both impurity ions.     

The X2Π and A2Σ+ states of FH+, ClH+ and BrH+: theoretical study of their g -factors and fine/hyperfine structures

Theoretical calculations on the fine, hyperfine and Zeeman (g-factor) parameters are reported for the X²Π and A²Σ⁺ states of FH⁺, ClH⁺ and BrH⁺. The fine-structure constants [spin–orbit (A), Λ-doubling (p, q) and spin–rotation constants (γ _Π, γ _Σ)] are evaluated up to second order (via SO/L couplings with several excited states) using a multireference configuration interaction (MRCI) method, a Breit–Pauli Hamiltonian and 6-311++(2d,2pd) basis sets. Hyperfine constants of magnetic and electric type [Frosch–Foley (a, b, c, d) and nuclear quadrupole (eQq ₀, eQq ₂)] are studied with density functional methods and various basis sets. Magnetic dipole moments (parameterized via g-factors) are calculated in second order like the fine structure constants. The situation is somewhat complex for X²Π since no less than five different g’s have to be evaluated in second order. In general, our results are in good agreement with those reported in the literature, mostly limited to the ground state. Our calculations confirm that, at equilibrium, all second-order properties are dominated by the couplings between the electronic states X and A.     

A study of the ground states of CaC2H2+,CaC2D2+ and CaC2H4+

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Crystal structure and properties of FeSr2NdCu2O7+δ

The compound FeSr₂NdCu₂O₇₊ (Fe1212) was successfully synthesized by solid-state reaction. X-ray diffraction data indicate that the sample is of single phase. Rietveld whole-pattern-fitting method was used to refine the crystal structure of samples prepared under different annealing conditions using the tetragonal system with space group P4/mmm. Magnetization measurements indicate that magnetic susceptibility changes with temperature in a Curie-type manner. Resistance measurements indicate that these samples have a semiconductor-like behavior. PACS 61.10.Nz; 74.72.Jt     

Microstructure and flux distribution in both pure and carbon-nanotube-embedded Bi2Sr2CaCu2O8+δ superconductors

In order to improve pinning properties of bulk Bi₂Sr₂CaCu₂O_8+δ (Bi-2212) materials, samples of both pure Bi-2212 and Bi-2212 with carbon nanotubes embedded (CNTE Bi-2212) have been prepared by partial-melting processing. The preparation conditions are chosen so that a significant fraction of carbon nanotubes can be successfully embedded in the material, as indicated by thermogravimetric analysis. The microstructure and composition of non-superconducting second phases are found to be different in these two types of samples. By means of magneto-optical (MO) imaging, flux distributions in both types of samples are investigated up to T=77 K. The MO investigation reveals the propagation of a flux front in both pure and CNTE Bi-2212, showing that there is a strong coupling between grains (clusters) which enables the flow of inter-granular currents. This grain coupling persists in our field range of ±180 mT. In bulk non-textured ceramic high-T_c superconductors, the flux fronts caused by currents flowing through the entire sample are observed for the first time. Intra-granular current densities are obtained from the images as a function of grain size. The MO investigations have revealed the differences in the current densities caused by the presence of carbon nanotubes, showing that the carbon nanotubes are indeed functioning like columnar defects produced by heavy-ion irradiation. The increase of the flux penetration field is also a manifestation of the increase of the transport current density in the CNTE Bi-2212. The superconducting properties in our samples are very well reproducible.     

Zn2+-Schiff’s Base Complex as an “On–Off-On” Molecular Switch and a Fluorescence Probe for Cu2+ and Ag+ Ions

The present study presents a thorough theoretical analysis of the electronic structure and conformational preference of Schiff’s base ligand N,N-bis(2-hydroxybenzilidene)-2,4,6-trimethyl benzene-1,3-diamine (H₂L) and its metal complexes with Zn²⁺, Cu²⁺ and Ag⁺ ions. This study aims to investigate the behavior of H₂L and the binuclear Zn²⁺ complex (1) as fluorescent probes for the detection of metal ions (Zn²⁺, Cu²⁺ and Ag⁺) using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The six conformers of the H₂L ligand were optimized using the B3LYP/6–311?+??+?G** level of theory, while the L^?2-metal complexes were optimized by applying the B3LYP functional with the LANL2DZ/6–311?+??+?G** mixed basis set. The gas-phase and solvated Enol-cis isomer (E-cis) was found to be the most stable species. The absorption spectra of the E-cis isomer and its metal complexes were simulated using B3LYP, CAM-B3LYP, M06-2X and ωB97X functionals with a 6–311?+??+?G** basis set for C, O, N and H atoms and a LANL2DZ basis set for the metal ions (Zn²⁺, Cu²⁺ and Ag⁺). The computational results of the B3LYP functional were in excellent agreement with the experimental results. Hence, it was adopted for performing the emission calculations. The results indicated that metal complex (1) can act as a fluorescent chemosensor for the detection of Ag⁺ and Cu²⁺ ions through the mechanism of intermolecular charge transfer (ICT) and as a molecular switch “On–Off-On” via the replacement of Cu²⁺ by Ag⁺ ions, as proved experimentally.

     

Molecule opacities of X~2Σ~+, A~2Π, and B~2Σ~+ states of CS~+

Carbon sulfide cation(CS~+) plays a dominant role in some astrophysical atmosphere environments. In this work, the rovibrational transition lines are computed for the lowest three electronic states, in which the internally contracted multireference configuration interaction approach(MRCI) with Davison size-extensivity correction(+Q) is employed to calculate the potential curves and dipole moments, and then the vibrational energies and spectroscopic constants are extracted. The Frank–Condon factors are calculated for the bands of X~2~+Σ~+–A~2Π and X~2Σ~+–B~2Σ~+systems, and the band of X~2Σ~+–A~2Π is in good agreement with the available experimental results. Transition dipole moments and the radiative lifetimes of the low-lying three states are evaluated. The opacities of the CS~+ molecule are computed at different temperatures under the pressure of 100 atms. It is found that as temperature increases, the band systems associated with different transitions for the three states become dim because of the increased population on the vibrational states and excited electronic states at high temperature.     

主成分回归法同时测定Cu2+、Pb2+、Hg2+和Cd2+

研究了用双硫腙光度法结合多元线性回归技术直接分析水相中有毒重金属离子的方法.结果表明,在β-环糊精和非离子表面活性剂Triton X-100的存在下,金属离子-双硫腙配位体系具有更高的灵敏度和稳定性.使用多元线性回归技术,可以在多种干扰金属离子共存的条件下,不经萃取和化学分离直接分析4种常见的有毒重金属离子.     

High-resolution electron microscopy and electron diffraction on Bi2Sr2-x La x Ca n Cu1+n O6+2n+δ

Solid solutions, Bi₂Sr_2-x La _x CuO₆₊ withx< 1.3 and Bi₂Sr_2-x La _x CaCu₂O₈₊ with probablyx<1.3 are reported. Both solid solutions show considerable nonlinear changes in the unit cell dimensions and a change in the modulation vector from 4.7b to 3.5b forx=0 andx=1.2, respectively. It is shown that Bi₂Sr_2-x La _x CaCu₂O₈₊ shows sometimes the absence of the 0.54 nm period alonga, whereas the modulation remains, suggesting both features not to be correlated. The investigation of the solid solution Bi₂Sr_2-x La _x CaCu₂O₈₊ with probablyx<1.3 are reported. Both solid solutions show considerable nonlinear changes in the unit cell dimensions and a change in the modulation vector from 4.7b to 3.5b forx=0 andx=1.2, respectively. It is shown that Bi₂Sr_2-x La _x CaCu₂O₈₊ is severly hampered by the presence of the n=0 structure in the reaction product when one starts with stoichiometric mixture. This can be overcome by adding extra Ca and heating directly just below the melting point. However addition of Ca to the mixture leads to changes in the solid solution range, because Ca can replace Sr.     

Measurements and calculations of H2-broadening and shift parameters of water vapour transitions of the ν1 + ν2 + ν3 band

The water vapour line broadening and shifting for 97 lines in the ν₁ + ν₂ + ν₃ band induced by hydrogen pressure are measured with Bruker IFS 125 HR FTIR spectrometer. The measurements were performed at room temperature, at the spectral resolution of 0.01 cm^?1 and in a wide pressure range of H₂. The calculations of the broadening γ and shift δ coefficients were performed in the semi-classical method framework with use of an effective vibrationally depended interaction potential. Two potential parameters were optimised to improve the quality of calculations. Good agreements with measured broadening coefficients were achieved. The comparison of calculated broadening coefficients γ with the previous measurements is discussed. The analytical expressions that reproduce these coefficients for rotational, ν₂, ν₁, and ν₃ vibrational bands are presented.     

Dissociative excitation and ionisation in H 2 + — He collisions

Using a flight-time-difference method we measured the energy distributions of H-H⁺ and H⁺-H⁺ fragment pairs arising from collisional dissociation of 10keV H ₂ ⁺ ions incident on He. The distributions measured at an angle of 0.28° with respect to the beam direction have maxima at 4.3eV for H-H⁺ and at 8.7eV for H⁺-H⁺ in the center-of-mass frame. The sharp maximum of the angle distribution in the CM frame at right angles to the beam direction observed in experiments in which only protons are detected does not appear in this coincidence experiment. This supports an earlier assumption that this sharp maximum can be ascribed to dissociation by vibrational-rotational excitation.     

Effect of Ge4+ and Mg2+ doping on superconductivity,fluctuation induced conductivity and interplanar coupling of TlSr2CaCu2O7−δ superconductors

Substitution of Ge⁴⁺ in place of Cu in Tl_0.85Cr_0.15Sr₂CaCu_2?xGe_xO_7?δ (x = 0–0.6) showed initial increase in zero critical temperature value, T_{c zero} from 98 K (x = 0) to 100 K (x = 0.1) and in the range of 85–86 K for x = 0.2–0.3. The slow decrease in T_{c zero} is unexpected as tetravalent Ge⁴⁺ substitution is expected to strongly reduce hole concentration in the samples and suppress T_{c zero}. Excess conductivity analyses of resistance versus temperature data based on Asmalazov–Larkin (AL) theory revealed that the substitution induced 2D-to-3D transition of fluctuation induced conductivity with the highest transition temperature, T_2D–3D observed at x = 0.1. FTIR spectroscopy analysis indicates Ge⁴⁺ substitution cause reduction in CuO₂/GeO₂ interplanar distance while our calculation based on Lawrence–Doniach model revealed highest superconducting coherence length, ξ_c(0) and interplanar coupling, J at x = 0.3. On the other hand, substitution of divalent Mg²⁺ for Ca²⁺ in (Tl_0.5Pb_0.5)(Sr_1.8Yb_0.2)(Ca_1?yMg_y)Cu₂O₇ (y = 0–1.0), which is not expected to directly vary hole concentration, surprisingly caused T_{c zero} to increase from 89.6 K (y = 0) to an optimum value of 95.9 K (y = 0.6) before decreasing with further increase in y. Excess conductivity analyses showed 2D-to-3D transition of fluctuation induced conductivity for all samples where the highest T_2D–3D was at y = 0.4. Similar calculation revealed highest values of ξ_c(0) and J also at y = 0.4. FTIR analysis of the samples indicates inequivalent Cu(1)O(2)Pb/Tl lengths and possible tilting of CuO₂ plane as a result of Mg²⁺ substitution. The increased ξ_c(0) and J as a result of the Ge⁴⁺ and Mg²⁺ substitutions are suggested to contributed to sustenance of superconductivity above 80 K in the samples.     

Reaction mechanism of D + ND→N + D_2 and its state-to-state quantum dynamics

The quantum state-to-state calculations of the D + ND→N + D_2 reaction are performed on a potential energy surface of 4 A' state. The state-resolved integral and differential cross sections and product state distributions are calculated and discussed. It is found that the rotational distribution, rather than the vibrational distribution, of the product has an obvious inversion. Due to the fact that it is a small-impact-parameter collision, its product D_2 is mainly dominated by rebound mechanism, which can lead to backward scattering at low collision energy. As the collision energy increases, the forward scattering and sideward scattering begin to appear. In addition, the backward collision is also found to happen at high collision energy, through which we can know that both the rebound mechanism and stripping mechanism exist at high collision energy.     

Isotope effect in chemical shifts of μ+ and H+: MuBr versus HBr and MuHO versus H2O

The isotopic difference between the diamagnetic shielding of a positive muon (⁺) in ⁺ HBr and H₂O and the analogous shielding of protons is computed from first principles in free space and in Br₂ solution, using a self-consistent cellular cluster multiple scattering method (SC-CMS) for condensed matter and for the free molecules. The isotope shift of the chemical shift _is at the ⁺ in these molecules dissolved in liquid Br₂ is evaluated with the eigenfunctions and eigenvalues obtained using Ramsey's formalism. For HBr the computed chemical shifts _is are comparable with experiment and with the calculations of Breskman and Kanofsky and of Williams, and the solvent effect has the correct sign and order of magnitude. For H₂O, _is has also the correct sign and order of magnitude when compared with ⁺SR experiments.     

The ion-molecule reaction O+ (4S) + N2(X1Σ+) → NO+ (X1Σ +, v′) + N(4S) and the predissociation of the A2Σ+ and B2Π states of N2O+

The potential energy surfaces (PESs) for several electronic states involved in the reaction O⁺ (⁴S) + N₂(X¹Σ⁺) → NO⁺ (X¹Σ ⁺, v′) + N(⁴S) and the role of the ionic N₂O⁺ intermediate have been investigated by ab initio calculations. The ⁴A″ PES, which correlates with the ground state educts, has a barrier of about 1 eV, and therefore at low collision energies the reaction cannot take place adiabatically on this surface. However, the spin-orbit coupling in the entrance channel allows the system to pass into the Renner-Teller system of the X² Π electronic ground state of the N₂O⁺ intermediate. The reaction then proceeds on these surfaces up to the region in the exit channel where a similar coupling allows it to reach the product quartet asymptote. At collision energies higher than about 1 eV, the reaction proceeds mainly on the adiabatic PES of the ⁴A″ state. The A²Σ⁺ state of N₂O⁺ predissociates via a vibronic coupling with the B²Π state, and in bent structures via a spin-orbit coupling with the ⁴A″ component of the ⁴II state. The electronic structure of the B²Π state is found to be of crucial importance for the understanding of the reactive processes in low lying electronic states of N₂O⁺.     

Kinetics and dynamics of the S(1D2) + H2 → SH + H reaction at very low temperatures and collision energies

We report combined studies on the prototypical S(1D2) + H2 insertion reaction. Kinetics and crossed-beam experiments are performed in experimental conditions approaching the cold energy regime, yielding absolute rate coefficients down to 5.8 K and relative integral cross sections to collision energies as low as 0.68 meV. They are supported by quantum calculations on a potential energy surface treating long-range interactions accurately. All results are consistent and the excitation function behavior is explained in terms of the cumulative contribution of various partial waves.     

Electron spin relaxation of exchange coupled pairs of transition metal ions in solids. Ti2+–Ti2+ pairs and single Ti2+ ions in SrF2 crystals

EPR (X- and Q-band) and electron spin relaxation measured by electron spin echo method (X-band) were studied for ${\text{Ti}}^{2+}(S=1)$ and ${\text{Ti}}^{2+}''–''{\text{Ti}}^{2+}$ pairs in ${\text{SrF}}_2$ crystal at room temperature and in the temperature range 4.2–115 K. EPR spectrum consists of a strong line from ${\text{Ti}}^{2+}$ and quartets 2:3:3:2 from titanium pairs $(S=2)$. Spin-Hamiltonian parameters of the pairs are $g_{\parallel }=1.883$, $g_{\perp }=1.975$ and $D=0.036{\text{cm}}^{-1}$. Temperature behavior of the dimer spectrum indicates ferromagnetic coupling between ${\text{Ti}}^{2+}$. Spin–lattice relaxation of individuals ${\text{Ti}}^{2+}$ is dominated by the ordinary two-phonon Raman process involving the whole phonon spectrum up to the Debye temperature ${\Theta }_{\text{D}}=380\text{K}$ with spin–phonon coupling parameter equal to $215{\text{cm}}^{-1}$. Important contribution to the relaxation arises from local mode vibrations of energy $133{\text{cm}}^{-1}$. The pair relaxation is faster due to the exchange coupling modulation mechanism with the relaxation rate characteristic for ferromagnetic ground state of the pairs $1/T_1\propto [\exp (2J/\mathit{kT})-1{]}^{-1}$ which allowed to estimate the exchange coupling $J=36{\text{cm}}^{-1}$. The theories of electron–lattice relaxation governed by exchange interaction are outlined for extended spin systems, for clusters and for individual dimers. Electron spin echo decay is strongly modulated by coupling with surrounding ¹⁹F nuclei. FT-spectrum of the modulations shows a dipolar splitting of the fluorine lines, which allows the evaluation of the off-center shift of ${\text{Ti}}^{2+}$ in pair as 0.132 nm. The electron spin echo dephasing is dominated by an instantaneous diffusion at low temperatures and by the spin–lattice relaxation processes above 18 K.     

(2+1) Newton�CHooke Classical and Quantum Systems

We study the Newton?CHooke groups in (2+1)-dimensions. A complete classification of both classical and quantum elementary systems is achieved by explicit computation of coadjoint orbits and unitary irreducible representations of the extended (by central extensions) Newton?CHooke groups. In addition, we show the quantization à la Moyal of a classical system using the Stratonovich?CWeyl correspondence. An analysis of the origin of the ??exotic?? central extension, which only appears in (2+1)-dimensions, is presented.