2010 Vol. 23, No. 4

2010, 23(4): 1-1. doi: 10.1088/1674-0068/23/4/1-1
The vector correlations between products and reagents for the title reactions have been calculated by the quasi-classical trajectory method at a collision energy of 21.32 kJ/mol on an accurate potential energy surface of Ho et al. (J. Chem. Phys. 119, 3063 (2003)). The peaks of the product angular distribution are found to be in both backward and forward directions for the two title reactions. The product rotational angular momentum is not only aligned, but also oriented along the negative direction of y-axis. These theoretical results are in good agreement with recent experimental findings for the two title reactions. The isotopic effect is also revealed and primarily attributed to the difference of the mass factor in the two title reactions.
The oxidative cyclization reaction of 2-nitroaniline via sodium hypochlorite to yield benzo-furoxan is investigated by the hybrid density functional theory B3LYP/6-31G(d,p) method. Solvent effects are estimated with the polarizable continuum model to optimize structures. The title reaction is predicted to undergo two pathways, each of which is a stepwise process.Path A includes four steps, namely oxidization, H-attack, hydrolysis, and cyclization. Path B involves the nucleophilic attack of OH- to the H atom of the N-H bond and the proton transfer to the N atom of amino group leading to the cleavage of the N-H single bond in the amino group. The calculated results indicate that path A is favored mechanism for the title reaction. Furthermore, it is rational for one water molecule serving as a bridge to assist in the hydrolysis step of Path A and our calculations exhibit that this process is the rate-determining step.
states of Fermi-resonance coupling vibrations in molecule CS2. It is demonstrated that those fidelities are dominant-positively correlated with each other, one of which by Wang et al. (Phys. Lett. A 373, 58 (2008)) is the most striking in dominant anti-correlation with quantum mutual entropy. That is useful for molecular quantum computing and quantum information.
The geometrical structures of wurtzite CrX (X=As, Sb, O, Se, and Te) were optimized, then their electric and magnetic properties were investigated by the ˉrst-principle calculations within the generalized gradient approximation for the exchange-correlation functional based on the density functional theory. These Cr-phosphides and Cr-sulphides were predicted to be half-metallic ferromagnets whose spin-polarization at the Fermi level is absolutely 100%.The molecular magnetic moments of Cr-phosphides and Cr-sulphides are 3.00 and 4.00 μB, which arise mainly from Cr-ions, respectively. There is ferromagnetic coupling in both Cr-phosphides and Cr-sulphides. The Curie temperatures of Cr-sulphides and Cr-phosphides are high. The electronic structures of Cr-ions are a21g↑↓t41u↑↓t11u e2g↑in Cr-phosphides and a21g↑↓t41u↑↓t11u↑t32g↑in Cr-sulphides, respectively.
The mechanism of the cycloaddition reaction of forming germanic bis-heterocyclic compound between singlet dichloro-germylene carbene and formaldehyde has been investigated with CCSD(T)//MP2/6-31G* method, from the potential energy profile, we predict that the re-action has two competitive dominant reaction pathways. The presented rule of this reaction: the 2p unoccupied orbital of the C atom in dichloro-germylene carbene insert the π orbital of formaldehyde from oxygen side, resulting in the formation of intermediate. In the interme-diate and between two reactants, because of the two bonding π orbital in dichloro-germylene carbene and formaldehyde have occurred [2+2] cycloaddition reaction, forming two four-membered ring compounds in which Ge and O are in the opposite orientation and in the syn-position, respectively. Because of the unsaturated property of C atom from carbene in the two four-membered ring compounds, they further reacts with formaldehyde, resulting in the generation of two germanic bis-heterocyclic compounds.
Cobalt-doped gold clusters AunCo (n=1~7) are systematically investigated for the possible stable geometrical configurations and relative stabilities of the lowest-lying isomers using density-functional theory at B3LYP/LanL2DZ level. Several low-lying isomers were deter-mined, and many of them are in electronic configurations with a high spin multiplicity. The results indicate that the ground-state AunCo (n=1~7) clusters adopt a planar structure except for n=7. The stability trend of the AunCo (n=1~7) clusters shows that the Au2Co clusters are magic cluster with high stability.
The geometries, stabilities, electronic, and magnetic properties of AunSc clusters have been systematically investigated by density functional theory. The lowest energy structures of AunSc favor planar structure and the doped Sc atom does not disturb the frame of Aunclusters with n≤11. For n≥12, Sc atom is fully encapsulated by the Au cages. From theanalysis of the second-order energy difference, the fragmentation energies, vertical ionizationpotential, vertical electron affinity, and HOMO-LUMO gap, the clusters with odd Au atoms possess relatively higher stabilities than their neighbor size. The doping of Sc atom can greatly improve the stability and change the sequence of chemical activity for Aun. For n≤11, the total magnetic moments of AunSc appear the alternation between 0.00 and 1.00 μB. The total magnetic moments are quenched when Sc is trapped into the Au cages with n≥12.
We report the observation of asymmetric switching dual peaks in ferroelectric copolymer films. These dual peaks occurs when the poling electric field is just below the coercive field and can be removed by continuous application of high enough switching voltage. Our experimental observations can be explained by the injection and the redistribution of space charges in ferroelectric films.
We investigated growth of GaN pn-junction layers grown on silicon(111) by plasma-assisted molecular beam epitaxy system and its application for photo-devices. Si and Mg were used as n- and p-dopants, respectively. The reflection high energy electron diffraction images indicated a good surface morphology of GaN pn-junction layer. The thickness of GaN pn-junctions layers was about 0.705 nm. The absence of cubic phase GaN showed that this layer possessed hexagonal structure. According to XRD symmetric rocking curve ω/2θ scans of (0002) plane at room temperature, the full width at half-maximun of GaN pn-junction sample was calculated as 0.34o, indicating a high quality layer of GaN pn-junction. Surprisingly, there was no quenching of the A1(LO) peak, with the presence of Si- and Mg-dopants in sample. The pn-junctions sample has a good optical quality which was measured by thephotoluminescence system. For photo-devices applications, Ni and Al were used as front and back contacts, respectively. The current-voltage characteristics of the devices showed the typical rectifying behavior of heterojunction. The photo-current measurement was performed using a visible-lamp under forward and reverse biases. From the temperature-dependent measurements, the current at low bias exhibited much stronger temperature dependence and weaker field dependence. The effect of thermal annealing on front contact Ni was also carried out. The front contact Ni was annealed at 400 and 600 oC for 10 min in the nitrogen ambient. The results showed that 600 oC treated sample had a higher gain at 1.00 V/e than 400 oC treated and untreated samples.
A novel N-doped TiO2 (N1-N2-TiO2) with substitutional and interstitial N impurities simul-taneously was successfully synthesized.The catalyst was characterized by X-ray diffraction,X-ray photoelectron spectroscopy, diffuse reflectance spectroscopy, photoluminescence, and electron paramagnetic resonance. The results demonstrated that the nitrogen was substi-tuted for the lattice oxygen atoms, and was also interstitially doped into the TiO2 lattice.The photocatalytic tests indicated that the N1-N2-TiO2 showed the highest photocatalytic activities of all the N-doped TiO2 under visible light, attributing to the synergetic effect of substitutional and interstitial nitrogen of N-doped TiO2.
The effects of O2 and the supported Pt nano-particles on the mechanisms and kinetics of the carbon support corrosion are investigated by monitoring the CO2 production using differential electrochemical mass spectrometry in a dual-thin layer flow cell. Carbon can be oxidized in different distinct potential regimes; O2 accelerates carbon oxidation, the rates of CO2 production from carbon oxidation in O2 saturated solution are two times of that in N2 saturated solution at the same potential; Pt can catalyze the carbon oxidation, with supported Pt nanoparticles, the overpotential for carbon oxidation is much smaller than that without loading in the carbon electrode. The mechanism for the enhanced carbon oxidation by Pt and O2 are discussed.
Large scale homogenous growth of microcrystalline silicon (μc-Si:H) on cheap substrates by inductively coupled plasma (ICP) of Ar diluted SiH4 has been studied. From XRD and Raman spectrum, we find that substrates can greatly affect the crystalline orientation, and the μc-Si:H films are comprised of small particles. Thickness detection by surface profilom-etry shows that the thin μc-Si:H films are homogenous in large scale. Distributions of both ion density and electron temperature are found to be uniform in the vicinity of substrate by means of diagnosis of Langmuir probe. Based on these experimental results, it can be proposed that rough surfaces play important roles in the crystalline network formation and Ar can affect the reaction process and improve the characteristics of μc-Si:H films. Also, ICP reactor can deposit the thin film in large scale.
High-efficient production of hydrogen from bio-oil was performed by electrochemical catalytic reforming method over the CoZnAl catalyst. The influence of current on the hydrogen yield, carbon conversion, and products distribution were investigated. Both the hydrogen yield and carbon conversion were remarkably enhanced by the current through the catalyst, reaching hydrogen yield of 70% and carbon conversion of 85% at a lower reforming temperature of 500 oC. The influence of current on the properties of the CoZnAl catalyst was also characterized by X-ray diffraction, X-ray photoelectron spectroscopy, thermal gravimetric analysis, and Brunauer-Emmett-Teller measurements. The thermal electrons would play an important role in promoting the reforming reactions of the oxygenated-organic compounds in the bio-oil.
The structure and crystal phase of the nanocrystalline powders of Ni1-xCdxFe2O4 (0≤x≤0.5) mixed ferrite, synthesized by wet chemical co-precipitation method, were characterized by X-ray diffraction. Results showed that the lattice parameter increased with increasing Cd concentration. Microstructure was studied by scanning electron microscopy. TG/DTA stud-ies were carried out on co-precipitated sulphate complexes. These studies revealed the low ferritization temperature (650 oC) of the ferrite system synthesized by presently adopted route of synthesis and occurrence of simultaneous decomposition and ferritization processes.Further studies by infrared spectroscopy were also conducted. Moreover, magnetic properties of the prepared nanoparticles were studied by magnetization and a.c. susceptibility mea-surements. The response of prepared Ni1-xCdxFe2O4 mixed ferrites to magnetic field was investigated. Results show that, magnetic susceptibility, Curie temperature, and effective magnetic moment decreased as the Cd content increases.
A low cost spin coating route of fabricating CuInS2 polycrystalline thin films by reactive sin-tering method was put forward. The ink for spin coating was optimized by pre-reducing the precursor powders in hydrogen, which turned the nanoparticle precursor powders from mixed sulfides into a mixture of CuInS2 and Cu-In metal alloys. The results of scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction, and Raman spectra showed that this optimization could highly improve the performance of CuInS2 polycrystalline thin films, including higher packing density, less impurity phases, and better quality. The en-ergy gap of optimized CuInS2 thin film was determined to be about 1.45 eV by absorption spectroscopy measurement.
Mn doped ZnO nano-crystallites were synthesized by state of the art sol-gel derived auto-combustion technique. As-burnt powder was investigated with different characterization techniques to explore the properties of Mn doped ZnO dilute magnetic semiconductor. X-ray diffraction measurements indicate that Mn doped ZnO retain wurtzite type hexagonal crystal structure like ZnO. Compositional and morphological studies were carried out by energy dispersive X-ray analysis and scanning electron microscopy, respectively. Tempera-ture dependent resistivity of the sample exhibited the semiconducting behavior of the DMS material. Room temperature magnetic properties determined by vibrating sample magne-tometer, revealed the presence of ferromagnetic and diamagnetic contributions in Mn doped ZnO.
Functionalized ionic liquid samples (bmim-PW12) were synthesized by 1-butyl-3-methyl-imidazolium bromide (bmimBr) and 12-phosphotungstic heteropolyacid (PW12). The sam-ples were annealed at 100-450 oC and were characterized by Fourier transform infrared spec-troscopy, X-ray diffraction, scanning electron microscope, thermal gravity-DTG, brunauer emmett teller, and NH3-temperature programmed desorption. The results showed that the bmim-PW12 samples were crystal and maintained intact Keggin structure. The organic parts of those samples were partly decomposed at a temperature more than 350 oC. The sample annealed at 400 oC exhibited nano-porous structure, strong acidity, and excellent catalytic activity on the esterification of n-butanol with acetic acid. The higher ester yield was ob-tained when the mass ratio of catalyst over the reactants amount was 5% for bmim-PW12 catalyst annealed at 400 oC.
The ordered bimodal mesoporous silica MCM-48 spheres were facile synthesized by mild-temperature post-synthesis H2O2 hydrothermal treatment of as-synthesized MCM-48. The results showed that H2O2 is indispensable for simultaneously removing organic templates and forming ordered bimodal mesoporous silica MCM-48 spheres. The bimodal mesoporous MCM-48 was characterized by X-ray diffraction, transmission electron micrographs, FT-IR, and N2 adsorption-desorption, and a possible mechanism was proposed for the formation of bimodal mesoporous MCM-48.
Oriented aggregation of nanoparticles has been accomplished by means of solid state reac-tion. Non-crystallized and crystallized ZnO nanoparticles/clusters could be accommodated in the lamellar spacing of inorganic-organic composite, which were prepared by thermolysis of layered solid zinc-oleate complex at 260 and 300 oC in air, respectively. High-resolution transmission electron microscopy and selected area electron diffraction patterns indicate that aggregates are single crystals with various defects. The photoluminescence excitation spectra of both samples show two bands at 272 and 366 nm. The former may originate from electron transfer from valence band to conduction band in ZnO clusters composed of less than 200 ZnO molecules (2R<2 nm).
The cationic guar (CG) is synthesized and the rheological behavior of aqueous solutions of CG in the presence of sodium dodecyl sulfate (SDS) is studied in detail. The steady viscosity measurements show that the zero shear viscosity enhancement can be almost 3 orders of magnitude as the concentration of SDS increases from 0 to 0.043%. The gel-like formation is observed as the concentration of SDS is greater than 0.016%. The oscillatory rheological measurements of CG solutions in the presence of SDS show that the crossover modulus is almost independent of the concentration of SDS whereas the apparent relaxation time increases swiftly upon increasing the concentration of SDS. The experimental results indicate that the strength rather than the number of the cross-links is greatly affected bySDS molecules. The mechanism concerning the effect of SDS upon the rheology of CG solutions can be coined by the two-stage model. Before the formation of cross-links at the critical concentration, the electrostatic interaction between SDS and cationic site of CG chains plays a key role and the SDS molecules bind to CG chains through the electrostatic interaction. After the formation of cross-links at the concentration greater than the critical concentration, the cooperative hydrophobic interaction become dominant and SDS molecules bind to the cross-links through the hydrophobic interaction. The rheological behavior of aqueous solutions of CG in the presence of SDS is chiefly determined by the micelle-like cross-links between CG chains. In fact, the flow activation energy of CG solution, obtained from the temperature dependence of the apparent relaxation time, falls in the range of transferring a hydrophobic tail of SDS from the micelle to an aqueous environment.
We describe a collinear velocity-map photoelectron imaging spectrometer, which combines a Wiley-McLaren time-of-flight mass analyzer with a dual-valve laser vaporization source for investigating size-selected cluster and reaction intermediate anions. To generate the reaction anions conveniently, two pulsed valves and a reaction channel are employed instead of premixing carrier gas. The collinear photoelectron imaging spectrometer adopts modified velocity-map electrostatic lens, and provides kinetic energy resolution better than 3%. The performance of the instrument is demonstrated on the photodetachment of Si4- at 532 and 355 nm, and Si3C- at 532 nm, respectively. In both cases, photoelectron spectra and anisotropy parameters are obtained from the images. For Si4-, the spectra show two well-resolved vibrational progressions which correspond to the ground state and the first excited state of the neutral Si4 with peak spacing of 330 and 312 cm-1, respectively. Preliminary results suggest that the apparatus is a powerful tool for characterizing the electronic structure and photodetachment dynamics of cluster anions.