Electronic structures and chemical bonding in diatomic ScX to ZnX (X = S, Se, Te)

Bond distances, vibrational frequencies, electron affinities, ionization potentials, dissociation energies, and dipole moments of the title molecules in neutral, positively, and negatively charged ions were studied using density functional method. Ground electronic state was assigned for each molecule. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that, besides ionic component, covalent bonds are formed between the metal s, d orbitals, and the p orbital of S, Se, and Te. For neutral and cationic molecules, the covalent character increases from ScX to CrX and from FeX to CuX with an exception of decrease at MnX and ZnX, while for anionic molecules, the trend is not obvious. For both neutral and charged molecules, the sulfides have the shortest bond distance and largest vibrational frequency, while tellurides have the largest bond distance and smallest vibrational frequency. For neutral and anionic molecules, the dissociation energy of sulfides is the largest, that of tellurides is the smallest, while this only remains true for cationic molecules from ScX+ to FeX+.

C-H activation motivated by N,N '-diisopropylcarbodiimide within a lutetium complex stabilized by an amino-phosphine ligand

A lutetium bis( alkyl) complex stabilized by a flexible amino phosphine ligand LLu( CH2Si(CH3)(3))(2)(THF) (L = (2,6-C6H3( CH3)(2)) NCH( C6H5) CH2P(C6H5)(2)) was prepared which upon insertion of N, N'-diisopropylcarbodiimide led to C-H activation via metalation of the ligand aryl methyl followed by reduction of the C=N double bond.

Tunable synthesis, growth mechanism, and magnetic properties of La0.5Ba0.5MnO3

La0.5Ba0.5MnO3 products with novel flowerlike, microcube, and nanocube structures were successfully synthesized by a simple hydrothermal route by controlling the alkalinity of the reaction solutions. The synthesized products were systematically studied by X-ray powder diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The results showed that the formation of the flowerlike structures with a layer assembly experienced a nucleation-aggregation-crystallization growth process, while the cubic structures experienced a nucleation-crystallization growth process due to the effect of different alkalinity in the reaction solutions. The higher alkalinity also led to a decrease in the size in the cubic structures. Suitable temperature and pressure were demonstrated to be crucial to the formation of the flowerlike structures by carrying out further control experiments. The measurement of the magnetic properties of three samples obtained at different alkaline conditions indicated that the size of the La0.5Ba0.5MnO3 products had an obvious influence on their properties; however, the dependence of the properties upon the morphology of the La0.5Ba0.5MnO3 products was minor.

Hydrothermal synthesis of Fe and Mn doped SnO2 and its magnetic structures

The dilute magnetic semiconductor of Sn1-x-yMnxFeyO2 (0 <= x <= 0.10, 0 <= y <= 0.10) Were syhthesized with the hydrothermal method using SnCl4, Mn(CH3COO)(2) center dot 4H(2)O and FeCl3 center dot 6H(2)O as the raw materials. The structure, morphologies and magnetic properties of the sample were characterized via X-ray powder diffractometer(XRD), transmission electron microscopy(TEM), Raman spectrum and superconducting and quantum interference device(SQUIT), and Mossbeaur spectrum. No secondary phase was found in the XRD spectrum. The morphology of the samples is affected by the kind or the mount of transition metal. The local vibrating model-of Mn Positioned SnO2 sites was found in Raman spectrum. The measured magnetic results indicate that when x = 0.10, y = 0, the sample exhibits strong magnetization in low-temperature (5 K), but the magnetization decrease rapidly at room. temperature; In contrast, when x = 0, y = 0.1, the sample's magnetization and coercivity are both small, but being temperature independent. Mossbeaur spectra indicates that part of the Fe is ferromagnetic coupled, and the simulating results indicate that the ferromagnetic character is intrinsic.

Reversible addition-fragmentation chain transfer mediated radical polymerization of asymmetrical divinyl monomers targeting hyperbranched vinyl polymers

Reversible addition-fragmentation chain transfer (RAFT) mediated radical polymerizations of allyl methacrylate and undecenyl methacrylate, compounds containing two types of vinyl groups with different reactivities, were investigated to provide hyperbranched polymers. The RAFT agent benzyl dithiobenzoate was demonstrated to be an appropriate chain-transfer agent to inhibit crosslinking and obtain polymers with moderate-to-high conversions. The polymerization of allyl methacrylate led to a polymer without branches but with five- or six-membered rings. However, poly(undecenyl methacrylate) showed an indication of branching rather than intramolecular cycles. The hyperbranched structure of poly(undecenyl methacrylate) was confirmed by a combination of H-1, C-13, H-1-H-1 correlation spectroscopy, and distortionless enhancement by polarization transfer 135 NMR spectra. The branching topology of the polymers was controlled by the variation of the reaction temperature, chain-transfer-agent concentration, and monomer conversion. The significantly lower inherent viscosities of the resulting polymers, compared with those of linear analogues, demonstrated their compact structure,

Polymerization of rac-lactide using schiff base aluminum catalysts: Structure, activity, and stereoselectivity

A series of aluminum ethyls and isopropoxides based upon N,N,O,O-tetradentate Schiff base ligand framework have been prepared. X-ray diffraction analysis and H-1 NMR confirmed that these Schiff base aluminum ethyls and isopropoxides were all monomeric species with a five-coordinated central aluminum in their solid structures. Compared to the aluminum ethyls which all retain their monomeric structure in the solution, the dinucleating phenomenons of aluminum isopropoxides with less steric hindered substituents in the solution have also been observed. The activities and stereoselectivities of these complexes toward the ring-opening polymerization of rac-lactide have been investigated. Polymerization experiments indicated that (SB-2d)(AlOPr)-Pr-i [(SB-2d) = 2,2-dimethyl-1,3-propylenebis(3,5-di-tert-butylsalicylideneiminato)] exhibited the highest stereoselectivity and (SB-3b)(AlOPr)-Pr-i [(SB-3b) = 2,2-dimethyl-1,3-propylenebis(3,5-dichlorinesalicylideneiminato)] possessed the highest activity among these aluminum isopropoxides. The substituents and the mode of the bridging part between the two nitrogen atoms both exerted significant influences upon the progress of the polymerizations, influencing either the tacticity of isolated polymers or the rate of polymerization.

Structural and magnetic properties of Sr2Fe1−xGaxMoO6 (0≤x≤0.25)

We have investigated the structure, magnetization and magnetoresistance (MR) of the double perovskite compounds Sr2Fe1−xGaxMoO6 (0≤x≤0.25). Rietveld refinement results show that the anti-site defects (ASDs) concentration increases with x, giving rise to highly disordered samples at the B/B positions, for the highest doping levels. The evolution of bond lengths and ions oxidation states could be understood by the distribution of trivalent Ga ions at the B/B positions, which leads to the formation of more disorder structure. The saturation magnetization and Curie temperature decreased with the Ga content increases in the samples, and their origin was found that the cations disorder for the Ga-doped compounds is annihilating double exchange mechanism due to the presence of significant amounts of Fe and Ga cations on the B site. The low-field magnetoresistance of Sr2FeMoO6 (SFMO) can be greatly enhanced by replacing the Fe by the nonmagnetic Ga ion up to a temperature of 300 K,since Ga ions may act as a barrier for electron transport along the chain in the ferromagnetic segregation and weaken the ferromagnetic exchange.

Luminescent supramolecular polymers: Cd2+-directed polymerization and properties

A family of supramolecular polymers was prepared via Cd2+-directed self-assembly polymerization of his (2,2':6',2 ''-terpyridine)-based ligand monomers, using oligofluorenes and triphenylamine as bridges under mild conditions. The polymers were fully characterized using thermogravimetric analysis, inherent viscosity, electrochemical measurements, UV-visible spectroscopy, photoluminescence (PL) and electroluminescence (EL). Polymers with oligofluorenes as spacers exhibited blue emission (434-442 nm) in dimethyl acetamide (DMAc) solution, while polymers with triphenylamine as spacer presented an emission peak at 494 nn in DMAc solution. Complexation polymerization of bis(2,2':6',2 ''-terpyridine)-based ligand monomers with cadmium(II) improved fluorescence quantum yields dramatically, and the film PL quantum yields of these polymers were about 0.38-0.54. Single-layer light-emitting diodes were fabricated with the configuration indium tin oxide (ITO)/polymer/Ca/Al; the EL showed green emission and the onset voltages of the devices were 8-11 V.

Electronic structures of MCO (M = Nb, Ta, Rh, Ir, Pd, Pt) molecules by density functional theory

Equilibrium geometries, vibrational frequencies, and dissociation energies of the transition metal carbonyls MCO (M = Nb, Ta, Rh, Ir, Pd, Pt) were studied by use of diverse density functional methods B3LYP, BLYP, B3P86, B3PW91, BHLYP, BP86, and PBE1PBE. It was found that the ground electronic state is (6)Sigma(+) for NbCO and TaCO, (2)Sigma(+) for RhCO,(2)Delta for IrCO, and (1)Sigma(+) for PdCO and PtCO, in agreement with previous theoretical studies. The calculated properties are highly dependent on the functionals employed, in particular for the dissociation energy. For most of the molecules, the predicted bond distance is in agreement with experiments and previous theoretical results. BHLYP is the worst method in reproducing the experimental results compared with the other density functional methods for the title molecules.

Electronic structures of Al2W, AlW2 clusters and their anions

Possible structures for Al2W and AlW2 clusters and their anions were presented and studied by use of density functional theory B3LYP at various spin multiplicities. The proposed three structures are triangular form with C-2v symmetry; linear structure with D (infinity h) symmetry; and linear structure with C (infinity v) symmetry. The calculated results indicate that structures with C-2v symmetry are the most stable for both neutral clusters and their anions. For Al2W, C-2v Symmetry at spin multiplicity 5 is the ground state, while for its anion, doublet is the lowest. For AlW2 and its anion, doublet and triplet are the ground states, respectively.

Electronic structures of hafnium dimer and trimer by density functional theory

Equilibrium geometries, vibrational frequencies and dissociation energies of hafnium dimer and trimer were studied by density functional methods B3LYP, BLYP, B3PW91, BHLYP, BP86, B3P86, mPW1PW91 and PBE1PBE. The results indicate that singlet is the ground state both for hafnium dimer and for trimer. For hafnium dimer, the calculated bond distance is less sensitive to the methods used. Except at BHLYP level, the calculated vibrational frequency is comparable to the experimental value. For hafnium trimer, equilateral triangle with D-3h symmetry is slightly favored compared with isosceles triangle with C-2v, symmetry except at BHLYP level. This conclusion is in agreement with experiment in which the ground state of Hf-3 is fluxional and low-spin or closed shell is preferred.

Density-functional study of lanthanum, ytterbium, and lutetium dimers

La-2, Yb-2, and Lu-2 have been studied by use of the density-functional methods B3LYP, BLYP, B3PW91, BHLYP, BP86, B3P86, MPW1PW91, and PBE1PBE. In these density-functional methods, the exchange functional is from either Becke's three-parameter HF-DFT hybrid exchange functional (B3), pure DFT exchange functional of 1988 (B), a modification of the half-and-half HF/DFT hybrid method (BH), Perdew-Wang 1991 (PW91), or Barone's modified PW91 (MPW1), while the correlation functional is from either Lee, Yang, and Parr (LYP), Perdew-Wang 1991 (PW91), or Perdew 86 (P86). PBE1PBE is the generalized-gradient-approximation exchange-correlation functional of Perdew, Burke, and Ernzerhof. For La-2, the calculated bond distance is in reasonable agreement with the experiment, but the calculated vibrational frequency is underestimated significantly compared with the experiment. Only BP86 and B3P86 have the best performance in reproducing the experimental dissociation energy for La-2. For the van der Waals dimer Yb-2, three functionals, B3LYP, BLYP, and BHLYP have excellent performance in reproducing the spectroscopic constants compared with both the experiment and previous theoretical studies.

Ground state of lutetium dimer by density functional methods

Bond distances, vibrational frequencies and dissociation energies for the ground state of Lu-2 were studied by density functional methods B3LYP, B3PW91, BLYP, BHLYP, BP86, B3P86, MPW1PW91, PBE1PBE and SVWN with CEP-121G and SDD basis sets. Singlet state is predicted to be the most stable. CEP-121G has a better overall performance than SDD. At CEP-121G basis set, all density functional methods used in this study perform well in reproducing the spectroscopic constants.

Extraction mechanism of La3+ from hydrochloric acid solution using Cyanex 302

The solvent extraction of La3+ from hydrochloric acid solutions was investigated using his (2, 4, 4-trimethylpentyl) monothiophosphinic acid (Cyanex 302, HL) as an extractant. The effect of equilibrium of aqueous acidity on extraction of La3+ using Cyanex 302 In different diluents was discussed. The effects of extractant concentration and chloride ion on the extraction reaction were also studied. Stoichiometry of the extraction reactions and the nature of metal complexes formed were determined using slope analysis technique and IR measurement.

Low-compressibility and hard materials ReB2 and WB2: Prediction from first-principles study

First-principle calculations are performed to investigate the structural, elastic, and electronic properties of ReB2 and WB2. The calculated equilibrium structural parameters of ReB2 are consistent with the available experimental data. The calculations indicate that WB2 in the P6(3)/mmc space group is more energetically stable under the ambient condition than in the P6/mmm. Based on the calculated bulk modulus, shear modulus of polycrystalline aggregate, ReB2 and WB2 can be regarded as potential candidates of ultra-incompressible and hard materials. Furthermore, the elastic anisotropy is discussed by investigating the elastic stiffness constants. Density of states and electron density analysis unravel the covalent bonding between the transition metal atoms and the boron atoms as the driving force of the high bulk modulus and high shear modulus as well as small Poisson's ratio.