Molecular structure,spectroscopic, and density functional theory studies of o-Dianisidine

o-Dianisidine has been characterized by the FT-IR, UV-Vis, and X-ray single-crystal determination. The compound crystallizes in the orthorhombic space group Pbca with a = 7.2593 (4) Å, b = 21.3485 (10) Å, c = 16.5835 (11) Å and Z = 8. Density functional theory has been used in the computation of the molecular geometry and harmonic vibrational wavenumbers. The calculated molecular geometry parameters have been compared with X-ray data. UV-Vis spectra of the compound have been predicted using the time-dependent density functional theory and good agreement between the calculated and experiment is determined. Besides, molecular electrostatic potential, frontier orbital analysis, and nonlinear optical properties were performed by using density functional theory calculations.     

Multinuclear NMR study of some organoplatinum complexes containing multifunctional azines as chelating ligands

1H-detected indirect NMR techniques were used to determine 15N and 195Pt NMR parameters for a series of organoplatinum(IV) complexes and one platinum(II) complex containing nitrogen-based azobispyridine, bispyridyltetrazine, and bipyrimidine ligands. The inverse technique permitted the detection of small 4J(Pt,H) and 5J(Pt,H) long-range couplings and the acquisition of 15N NMR data in natural isotopic abundance via nJ(N,H) intra- and inter-ligand couplings, but failed in cases where coherence transfer is quenched by rapid relaxation of the metal atom. In one case, analysis of satellite patterns in a set of 1H,15N, 1H,195Pt and 1H,13C correlation spectra allowed a positive sign to be determined for 1J(Pt,15N). Qualitative arguments are presented to explain the observed 15N coordination shifts in complexes with different azine ligands in terms of azine-M dative bond formation and LnM-azine back-donation.     

Complex reduction chemistry of (abpy)PtCl2, abpy = 2,2'-azobispyridine: formation of cyclic [(micro,eta2:eta1-abpy)PtCl]2(2+) with a new coordination mode for abpy and a near-infrared ligand-to-ligand intervalence charge transfer absorption of the one-electron reduced state

The structurally characterized (abpy)PtCl2, abpy = 2,2'-azobispyridine, reveals a strong metal/ligand pi interaction as supported by DFT calculations. Unexpectedly, its chemical or electrochemical reduction occurs irreversibly to yield EPR-detectable [(micro,eta2:eta2-abpy)[PtCl2]2]*- and, as the main product of chloride dissociation, the structurally identified and DFT-calculated dinuclear [(micro,eta2:eta1-abpy)PtCl]2(2+) with a novel coordination mode for abpy and isolated as tetrachlorozincate. Stepwise reversible one-electron reduction of that dimer, separated by 0.24 V, exhibits an intense near-infrared band for the monocationic intermediate [(abpy(-I))(abpy)Pt2Cl2]*+ at 1220 nm (epsilon = 3370 M(-1) cm(-1)) which is attributed to a ligand-to-ligand intervalence charge-transfer transition.     

Rapid separation on copper powder of total mercury in blood and determination of mercury by flameless atomic absorption spectrometry.

The determination of mercury in blood by flameless atomic absorption spectrometry (FAAS) has been described. Prior to its analysis, the sample was decomposed by combustion and separated on a copper powder micro-column. A special type of cell has been used which gives a better sensitivity compared with the types of cells described in the literature and the method of FAAS analysis has been improved. The sensitivity of 0.1 ng for 1% absorbance was observed and the standard deviation for six determinations at this level was found to be +/- 0.05 ng, for 95% probability.     

Thermodynamic Parameters of Cholesteric/Smectic A Transition in Cholesteric Myristate and Its Binary Mixture CM/PCPB

Thermodynamic properties of the cholesteryl myristate (CM) and its binary mixture CM/PCPB (p-pentylphenyl-2-chloro-4(p-pentylbenzoyl)-benzoate) are studied at the concentrations of x_PCPB = 0.052 and 0.219 as a function of temperature near the cholosteric/smectic A transition. By analyzing the observed molar volume from the literature, the temperature dependences of the thermal expansion, isothermal compressibility and the difference in the specific heat are calculated and, the Pippard relations are established for those compounds close to the cholesteric/smectic A transition. Predictions of the thermodynamic quantities and the Pippard relations can be examined by the experimental measurements of the CM and its binary mixture of CM/PCPB close to the cholesteric/smectic A transition.     

The barrier-height inhomogeneity in identically prepared Ni/n-type 6H-SiC Schottky diodes

The effective barrier heights and ideality factors of identically fabricated Ni/n-type 6 H-SiC Schottky diodes (23 dots) have been calculated from their experimental forward bias current–voltage (I–V) and reverse bias capacitance–voltage (C–V) characteristics. A statistical study related to the experimental barrier heights (BHs) and ideality factors of the diodes has been made. The effective Schottky barrier heights (SBHs) and ideality factors obtained from the I–V and C–V characteristics have differed from diode to diode. The BHs obtained from the I–V characteristics varied from 0.85 to 1.03 eV, the ideality factors varied from 1.13 to 1.40 and the BHs from C^-2–V characteristics varied from 1.10 to 1.70 eV. The experimental BH and ideality factor distributions obtained from the I–V characteristics are fitted by a Gaussian function, and their mean values are found to be 0.92±0.04 eV and 1.29±0.08 eV, respectively. The lateral homogeneous SBH value of 1.16 eV for the Ni/n-type 6H-SiC diodes has been calculated from a linear extrapolation of the effective barrier heights to n_if=1.03. PACS 79.40.+z; 73.40.Sx; 73.30.+y; 71.20.Nr     

Fringing field optimization of hemispherical deflector analyzers using BEM and FDM

In this paper we present numerical modeling results for fringing field optimization of hemispherical deflector analyzers (HDAs), simulated using boundary-element and finite-difference numerical methods. Optimization of the fringing field aberrations of HDAs is performed by using a biased optical axis and an optimized entry position offset (paracentric) from the center position used in conventional HDAs. The described optimization achieves first-order focusing thus also further improving the energy resolution of HDAs.     

Calculation of the surface tension of liquid Ga-based alloys

As known, Eyring and his collaborators have applied the structure theory to the properties of binary liquid mixtures. In this work, the Eyring model has been extended to calculate the surface tension of liquid Ga–Bi, Ga–Sn and Ga–In binary alloys. It was found that the addition of Sn, In and Bi into Ga leads to significant decrease in the surface tension of the three Ga-based alloy systems, especially for that of Ga–Bi alloys. The calculated surface tension values of these alloys exhibit negative deviation from the corresponding ideal mixing isotherms. Moreover, a comparison between the calculated results and corresponding literature data indicates a good agreement.