Insulator-to-metal transition in selenium-hyperdoped silicon: observation and origin

Hyperdoping has emerged as a promising method for designing semiconductors with unique optical and electronic properties, although such properties currently lack a clear microscopic explanation. Combining computational and experimental evidence, we probe the origin of sub-band-gap optical absorption and metallicity in Se-hyperdoped Si. We show that sub-band-gap absorption arises from direct defect-to-conduction-band transitions rather than free carrier absorption. Density functional theory predicts the Se-induced insulator-to-metal transition arises from merging of defect and conduction bands, at a concentration in excellent agreement with experiment. Quantum Monte Carlo calculations confirm the critical concentration, demonstrate that correlation is important to describing the transition accurately, and suggest that it is a classic impurity-driven Mott transition.     

Hydrogen Bonded Supramolecular Network from a Mixed Valence Cobalt System: Synthesis and Crystal Structure of [Co(H2O)6][Co(pydc)2(en)]2·14H2O

Abstract  

The [Co(H₂O)₆][Co(pydc)₂(en)]₂·14H₂O (1) compound (H₂pydc = Pyridine-2,3-dicarboxylic acid and en = ethylenediamine) was synthesized and characterized by elemental analysis, magnetic and spectroscopic measurements (UV–Vis and IR spectra) and single crystal X-ray diffraction technique. There are two coordination spheres with different charges inside this aqueous compound of ionic character. The cationic part is composed of Co(II) encircled by six aqua ligand. Whereas the anionic part contains two anions complex unit each with −1 charge and have Co(III) ions in the centre. As a result different coordination spheres have cobalt ions with different states. The crystallographic analysis revealed that 1 consists of both discrete one-cationic and two-anionic entities, [Co(H₂O)₆]²⁺ and [Co(pydc)₂(en)]₂⁻ and fourteen crystal water molecules. Two water molecules within the water cluster act as hydrogen-bonding acceptors, whereas one water molecule acts as a hydrogen-bonding donor to form a discrete water trimer. These water molecules have stabilized the crystal structure by strong hydrogen bonding interactions.     

MHD mixed convective heat transfer flow about an inclined plate

Mixed convection heat transfer about a semi-infinite inclined plate in the presence of magneto and thermal radiation effects is studied. The fluid is assumed to be incompressible and dense. The nonlinear coupled parabolic partial differential equations governing the flow are transformed into the non-similar boundary layer equations, which are then solved numerically using the Keller box method. The effects of the mixed convection parameter R _i, the angle of inclination α, the magnetic parameter M and the radiation–conduction parameter R _d on the velocity and temperature profiles as well as on the local skin friction and local heat transfer parameters. For some specific values of the governing parameters, the results are compared with those available in the literature and a fairly good agreement is obtained.     

Bis{(μ-acetato)[μ-bis(salicylidene)-1,3-propanediaminato]zinc(II)}zinc(II)

In the title linear trinuclear compound, [Zn{Zn(CH₃COO)(C₁₇H₁₆N₂O₂)}₂], the central Zn²⁺ ion, which is located on an inversion centre, has a distorted octahedral coordination involving four bridging O atoms from two N,N′-bis­(salicyl­idene)-1,3-propane­diaminate ligands in the equatorial plane and one O atom from each bridging acetate group in the axial positions. The coordination around the terminal Zn²⁺ ion is irregular square pyramidal, with two O and two N atoms of the ligand in the basal plane and one O atom from an acetate group in the apical position. The acetate bridges linking the central and terminal Zn²⁺ ions are mutually trans. The Zn⃛Zn distance is 3.0520 (8) Å. The relationship of this structure to that of [Zn{Cu(CH₃COO)(C₁₇H₁₆N₂O₂)}₂] is discussed.     

Complexation and transport of amino acid esters and their salts with synthesised chiral novel aza crown ether derivatives

The syntheses of four aza-15-crown-5 ethers bearing phenyl and phenoxymethyl moieties attached to a stereogenic centre on the crown ring were achieved. Macrocycles have exhibited strong binding ability (K_a = 5364–12,969 M^? 1) and modest enantiomeric discrimination towards the enantiomers of amino acid methyl ester salts by UV titration method in CHCl₃ at 25°C. Computer modelling results supported experimental data providing a detailed understanding of the molecular recognition mode between hosts and guests and the likely binding sites involved. Macrocycles were used for chiral discrimination of amino acids in their zwitterionic forms or as potassium and sodium salts in transport experiments across a bulk chloroform membrane with satisfactory selectivity.     

Lead Fractionation Analysis in Lipstick Samples by Inductively Coupled Plasma-Mass Spectrometry

A new analytical approach based on fractionation was introduced for lead in lipstick samples. Different separation techniques including n-hexane, glycerol extraction, and activated carbon adsorption were used to characterize the lipid fraction, polar and aromatic components of the samples. Additionally, artificial saliva and food stimulant extractions were used for the risk assessment studies. Trace metal levels in fractions were determined by inductively coupled plasma-mass spectrometry. Method validation parameters in the total element determinations were defined in terms of detection limits, accuracy, and precision. The limits of detection and quantification were 0.02 and 0.07 mg kg^?1 for Pb; whereas the repeatability and reproducibility of the results based on percent relative standard deviation were 3.0% and 7.2% for lead, respectively.     

Synthesis, structural, spectroscopic characterization, and structural comparison of 3-hydroxybenzoate and nicotinamide/N,N-diethylnicotinamide mixed ligand complexes with Zn(II)

The mixed-ligand 3-hydroxybenzoic acid complex of Zn(II) with nicotinamide and N,N-diethylnicotinamide were synthesized and characterized (colorless single crystals, [Zn(3-hba)₂(H₂O)₂(na)₂] and [Zn(3-hba)₂(H₂O)₂(dena)₂]). The chemical, FT-IR, thermal, mass spectral analyses, and X-ray data results revealed that both of the compounds contain two water molecules, two 3-hydroxybenzoate (3-hba) and two nicotinamide (na) or two N,N-diethylnicotinamide (dena) ligands per formula unit. 3-hba and na or dena ligands bind to the Zn(II) ion monodentately through their acidic oxygen and pyridinic nitrogen atoms, respectively. The coordination of metal atoms are completed by two molecules of aqua ligands. The charge balance of complexes is accommodated by two molecules of 3-hba ions. The unit cell has two molecules coordination molecules and each of them was as settled to four surfaces of unit cell cage in na complex. There is one mole molecule that was occupied to center of unit cell cage in dena complex. The two dimensional network structure of the complex is like a hexagonal for na and square plane for dena complexes. The thermal decomposition takes place in three steps; first, dehydration of the two aqua ligands, second, elimination of the two nicotinamide ligands, finally, burning of the two benzoate ion ligands.     

Experimental and computational studies on (<Emphasis Type=Italic>Z</Emphasis>)-1-((4-phenylamino)phenylamino)-methylene)naphthalen-2(1<Emphasis Type=Italic>H</Emphasis>)-one

The Schiff base compound (Z)-1-((4-phenylamino)phenylamino)methylene)naphthalen-2(1H)-one has been synthesized and characterized by IR, UV–Vis, and X-ray single-crystal determination. Molecular geometry from X-ray experiment of the title compound in the ground state have been compared using the Hartree–Fock (HF) and density functional method (B3LYP) with 6−31G(d,p) basis set. Calculated results show that density functional theory DFT and HF can well reproduce the structure of the title compound. Using the time-dependent density functional theory (TD-DFT) and Hartree–Fock (TD-HF) methods, electronic absorption spectra of the title compound have been predicted and a good agreement with the TD-DFT method and experimental ones is determined. The energetic behavior of the title compound in solvent media has been examined using B3LYP method with the 6−31G(d,p) basis set by applying the polarizable continuum model (PCM). The total energy of the title compound decreases with increasing polarity of the solvent. In addition, DFT calculations of the title compound, molecular electrostatic potential (MEP), natural bond orbital analysis (NBO), and non-linear optical (NLO) properties were performed at B3LYP/6−31G(d,p) level of theory.     

Effects on measurement of photon-atom scattering of applied pressures on sample at different thickness

N_coh/N_Comp and NK_β/NK_α intensity ratios of scattered photons by Zn in the linear region and the infinite mass thickness region are measured as functions of the pressure used for compressing the pellets with a Si(Li) detector using Am-241 and Fe-55 annular source. Besides, the effect on the experimental intensity ratio of relation between two different thicknesses of sample with applied different pressures on the sample is investigated in this study. Harmony between the linear and infinitive (critical) thickness region and the applied pressure on the sample has directly affected the experimental intensity ratios. Experimental results were not compared with various theoretical values in the literature, for present results constitute the first experimental measurements.     

Matrix Summability and Positive Linear Operators

In the present paper we prove a Korovkin type approximation theorem for a sequence of positive linear operators acting from a weighted space C_ρ1 into a weighted space B_ρ2 with the use of a matrix summability method which includes both convergence and almost convergence. We also study the rates of convergence of these operators.