2010 Vol. 23, No. 5

2010, 23(5): 1-1. doi: 10.1088/1674-0068/23/5/1-1
Four-, six-, and eight-membered ring silica nanotubes at temperatures from 300 K to 1600 Kare relaxed by classical molecular dynamics simulations with three potential models. Thesimulation results indicate that the stability of the end rings of the three silica nanotubes gradually decreases with increase in temperature. The validity of the vibrational features of silica nanotubes is shown by the vibrational density of states. Infrared spectra on the silica nanotubes under different temperatures are investigated. A detailed assignment of each spectral peak to the corresponding vibrational mode of the three nanotubes has been addressed. The results are in good agreement with the other theoretical and experimental studies.
An all-atom dimethyl sulfoxide (DMSO) and water model have been used for molecular dy-namics simulation. The NMR and IR spectra are also performed to study the structures and interactions in the DMSO-water system. And there are traditional strong hydrogen bondsand weak C—H…O contacts existing in the mixtures according to the analysis of the radial distribution functions. The insight structures in the DMSO-water mixtures can be classified into different regions by the analysis of the hydrogen-bonding network. Interestingly, the molar fraction of DMSO 0.35 is found to be a special concentration by the network. It is the transitional region which is from the water rich region to the DMSO rich region. The sta-ble aggregates of (DMSO)m·S=O…HW—OW·(H2O)n might play a key role in this region.Moreover, the simulation is compared with the chemical shifts in NMR and wavenumbers in IR with concentration dependence. And the statistical results of the average number hydrogen bonds in the MD simulations are in agreement with the experiment data in NMR and IR spectra.
The photodissociation of NO+ at c3∏(v′=0) state is studied by threshold photoelectron-photoion coincidence imaging method. By some assumptions, the relations between velocity in center of mass (CM) coordinates and most probable center of mass (MPCM) coordinates,time of flight and displacement in the velocity map image of fragment ions are derived using vector addition of velocity and displacement on the condition of perpendicular molecular beam. Using these relations the velocity in CM coordinates, the velocity and angular distri-bution of N+ fragment ions in MPCM coordinates are obtained and discussed, respectively.
The hydrodynamic instabilities driven by an acid-base neutralization reaction, in contact along a plane interface, placed in a Hele-Shaw cell under the gravitational field are reported.The system consists of the heavier aqueous tetramethyle-ammonium hydroxide below the lighter layer of organic phase with propionic acid as reacting specie. The effect of chemical composition on hydrodynamic instabilities during interfacial mass transfer accompanied by a neutralization reaction is investigated. Depending on the initial concentration of the reacting species, Marangoni convection in the form of roll cells or trains of waves is observed. Mach-Zehnder interferometer is used to measure the change in base concentration at the time of instability formation. The results show that the instabilities resulted from the convection flow are more efficient to the mechanism of mass transfer and can drastically alter pattern formation in the system.
The quasi-classical trajectory calculations O++DH (v=0, j=0)→OD++H reactions on the RODRIGO potential energy surface have been carried out to study the isotope effect onstereo-dynamics at the collision energies of 1.0, 1.5, 2.0, and 2.5 eV. The distributions of dihedral angle P(φr) and the distributions of P(θr) are discussed. Furthermore, the angular distributions of the product rotational vectors in the form of polar plot in θr and φr are calculated. The differential cross section shows interesting phenomenon that the reaction is dominated by the direct reaction mechanism. Reaction probability and reaction cross section are also calculated. The calculations indicate that the stereo-dynamics properties of the title reactions are sensitive to the collision energy.
First-principles calculations have been performed to clarify the differences of the electronic structures of Ga-doped ZnO and ZnS. Results show the local density approximation and local density approximation+U calculations are in good qualitative agreement with each other. After doping, impurity states appear near the Fermi level in both ZnO and ZnS cases.When ZnO is doped, the impurity states are delocalized in the whole conduction band. On the contrary, when ZnS is doped, though the p state of Ga is also delocalized, the s state is localized near the Fermi level. Partial charge density distributions of the frontier orbital show the same information. After an exchange of the crystal structures of ZnO and ZnS,results remain unchanged. The localized Ga s state accounts for the bad electrical properties of Ga-doped ZnS.
The mechanism of the cycloaddition reaction of forming a silicic bis-heterocyclic compound between singlet dimethylmethylenesilylene (Me2C=Si:) and ethene has been investigated with the CCSD(T)//MP2/6-31G* method. From the potential energy profile, it can be predicted that, this reaction has one dominant channel. The presented rule of this dominant channel: the 3p unoccupied orbital of Si in dimethylmethylenesilylene and the π orbital of ethene forming the π→p donor-acceptor bond, resulting in the formation of three-membered ring intermediate (INT1); INT1 then isomerizes to a four-membered ring silylene (P2), which is driven by ring-enlargement effect; due to sp3 hybridization of Si atom in P2, P2 further combines with ethene to form a silicic bis-heterocyclic compound.
The adsorption of isolated alkali metal atoms (Li, Na, K, Rb, and Cs) on defect-free sur-face of MgO(001) has been systemically investigated with density functional theory using a pseudopotential plane-wave approach. The adsorption energy calculated is about -0.72 eV for the lithium on top of the surface O site and about one third of this value for the other alkali metals. The relatively strong interaction of Li with the surface O can be explained by a more covalent bonding involved, evidenced by results of both the projected density of states and the charge density difference. The bonding mechanism is discussed in detail for all alkali metals.
Four methods, including voltammetric measurement of double layer capacitance, surface oxides reduction, under potential deposition of Cu and carbon monoxide (CO) stripping have been applied to evaluate the real surface area of a polycrystalline Pd (pc-Pd) electrode. The results reveal that the second and third methods lead to consistent results with deviations below 5%. And from the determined double layer capacitance and CO stripping charge, it is deduced that the double layer capacity unit area is 23.1±0.4 μF/cm2 and the saturated CO adlayer should be ca. 0.66 ML in order to ensure that the real surface area as determined isconsistent with the other two techniques. The applicability as well as the attentions when applying these techniques for the determination of the real surface area of pc-Pd electrodes have been discussed.
The first three-dimensional interaction potential energy surface (PES) of the Ar2-Ne complex is developed using the single and double excitation coupled cluster theory with noniterative treatment of triple excitations CCSD(T). The aug-cc-pVQZ basis sets are employed for all atoms, including an additional (3s3p2d2f1g) set of midpoint bond functions. The calculated single point energies are fitted to an analytic two-dimensional potential model at each of seven fixed rAr2 values. The seven model potentials are then used to construct the three-dimensional PES by interpolating along (r—re) using a sixth-order polynomial. The PES is used in the following rovibrational energy levels calculations. The comparisons of theoretical transition frequencies and spectroscopic constants with the experimental results are given.
The field emission from pure boron-nitride nanotube and boron-nitride nanotube encapsu-lated with natrium atoms with the electric field perpendicular to the axis of nanotubes is simulated based on a self-consistent method using the density-functional formalism. It has been found that the nearly-free-electron states in boron-nitride nanotube would perform very well in field emissions after natrium atom encapsulation. The characters of total en-ergy distribution curves are analyzed to seek the function of nearly-free-electron states in the field emission, with special attention to response of the emission current to the external electric field. At last, the perpendicular emission geometry is found to possess a very sensi-tive response degree which is supposed to be related to specific expansion orientation of the nearly-free-electron states in this system.
Spectral and photophysical investigations of 4′-(p-aminophenyl)-2,2′:6′,2′′-terpyridine (APT) have been performed in various solvents with different polarity and hydrogen-bonding ability.The emission spectra of APT are found to exhibit dual fluorescence in polar solvents, which attributes to the local excited and intramolecular charge transfer states, respectively. The two-state model is proven out for APT in polar solvent by the time-correlated single photon counting emission decay measurement. Interestingly, the linear relationships of different emission maxima and solvent polarity parameter are found for APT in protic and aprotic solvents, because of the hydrogen bond formation between APT and alcohols at the amino nitrogen N25. Furthermore, the effects of the complexation of the metal ion with tpy group of APT and the hydrogen bond formation between APT with methanol at the terpyridinenitrogen N4—N8—N14 are also presented. The appearance of new long-wave absorption and fluorescence bands indicates that a new ground state of the complexes is formed.
Adsorption behavior and electronic structure of tin-phthalocyanine (SnPc) on Ag(111) sur-face with Sn-up and Sn-down conformations are investigated using first-principles calcula-tions. Two predicted adsorption configurations agree well with the experimentally deter-mined structures. SnPc molecule energetically prefers to adsorb on Ag(111) surface with Sn-down conformation. The energy required to move the central Sn atom through the frame of a phthalocyanine molecule, switching from the Sn-up to Sn-down conformation, is about 1.68 eV. The simulated scanning tunneling microscopy images reproduce the main features of experimental observations. Moreover, the experimentally proposed hole attachment mech-anism is verified based on the calculated density of states of SnPc on Ag(111) with three different adsorption configurations.
The quasi-classical trajectory calculations based on extended London-Eyring-Polanyi-Sato potential energy surface have been used to study the reaction of Ba+HI→BaI+H system. The rotational, vibrational, translational, and angular distributions of the product BaI have been calculated. The calculated results are in good agreement with the experimental ones.
The infrared absorption and 514.5 nm excited Raman spectra were measured for the metallo-tetra-(tert-butyl)-tetraazaporphyrin (MT(tBu)TAP, M=Cu, Co, Ni, Zn). The ground-state structures and vibrational spectra of MT(tBu)TAPs have been calculated at the B3LYP level of theory. The observed Raman and IR bands have been assigned based on the calculation results and by comparing with the normal metalloporphyrins. The relationship between the Raman/IR frequencies and the structures of TAP ring was investigated. The results show that the frequencies of CβCβ′ stretch (Ag), asymmetric CαNm stretch (Ag), and symmetric CαNm stretch (Bg) modes increase linearly with the decrease of the core-sizes of TAP ring.Among the three modes, the later two are more sensitive to the core-size change.
Thin films of CuInS2 were grown on glass substrate by successive ionic layer adsorption and reaction method with different [Cu]/[In] ratios and annealed at 400 °C for 30 min. The crystal structure and grain sizes of the thin films were characterized by X-ray diffraction method. Atomic force microscopy was used to determine surface morphology of the films. Optical and electrical properties of these films were investigated as a function of [Cu]/[In]ratios. The electrical resistivity of CuInS2 of thin films was determined using a direct current-two probe method in the temperature range of 300—470 K. It is observed that, the electrical resistivity values show a big decreasing with increasing [Cu]/[In] ratio. Hence, the [Cu]/[In] ratio in the solution can drastically affect the structural, electrical, and optical properties of thin films of CuInS2.
The CuInSe2 absorber was synthesized by non-vacuum process with a simple and low-cost method, which fabricated absorber layer of thin-film solar cell. The extra amount of Se was added into the ink to help reduction of the oxide and solid Se fountain was used to provide Se atmosphere during the selenization progress. The influence of same factors was investigated, such as the time of reduction in H2, the time of selenization and the Se vapor pressure. The selenizaion, processed at 550 °C for 60 min with the Se vapor pressure at 1.90 kPa, resulted in high quality CuInSe2 layer with very good chemical composition.
Nanocrystalline Cu0.5Zn0.5Fe2-xAlxO2 (x=0.0, 0.1, 0.2, 0.3, 0.4, and 0.5) ferrite materials were synthesized using standard solid state reaction technique. The effects of Al3+ contents on the structural, electrical, and magnetic properties were investigated. Single phase cubic spinel structure was revealed by X-ray diffraction analysis. The crystallite size was evaluated considering the most intense diffraction peak (311) using Scherrer formula. Lattice constant decreased, whereas porosity increased with the increase in Al3+ concentration. The value of saturation magnetization decreased with increasing aluminum contents. Temperature dependent value of direct current electrical resistivity has been determined. It is observed that the substitution of Al3+ has significant impact on the dielectric constant, tangent of dielectric loss angle and dielectric loss factor. The variation in dielectric properties was attributed to space charge polarization.
Ag dendritic nanostructures were synthesized on fluorine-doped tin oxide covered glass sub-strates by the electrodeposition method. Results demonstrate that the size, diameter, crys-tallinity, and branch density of the Ag dendrites can be controlled by the applied potential,the surfactants and the concentration of AgNO3. Three kinds of typical silver dendrites were applied as substrates of the surface enhanced Raman scattering (SERS) and one of them was able to clearly detect rhodamine 6G concentrations up to 0.1 nmol/L. The differences of the SERS spectra at these Ag dendrites confirmed that the shapes and interparticle spacings have great effect on Raman enhancement, especially the interparticle spacings.
BaTiO3 powders are prepared by sol-gel method by cotton template. Polypyrrole is pre-pared by chemical oxidation route in the emulsion polymerization system. Then BaTiO3-polypyrrole composites with different mixture ratios are prepared by as-prepared material.The structure, morphology, and properties of the composites are characterized with Infrared spectrum, X-ray diffraction, scanning electron microscope, and net-wok analyzer. The com-plex permittivity and reflection loss of the composites are measured at different microwave frequencies in S-band and C-band (0.03—6 GHz) employing vector network analyzer model PNA 3629D vector. The effect of the mass ratio of BaTiO3 to polypyrrole on the microwave loss properties of the composites is investigated. A possible microwave absorbing mechanism of BaTiO3-polypyrrole composite is proposed. The BaTiO3-polypyrrole composite can find applications in suppression of electromagnetic interference and reduction of radar signature.
In the electric field and layer-to-layer interaction energy, the law of split-level of high-level Stark effect of spherical nanometer system is explored as well as the frequency of spectrum,intensity and size effect of coefficient of spontaneous radiation. Taking three layers CdS/HgS spherical nanometer system as an example, the influence of the electric field and layer-to-layer interaction energy is explored on Stark effect and spectrum. The results show that in the Stark effect system, the energy level is split based on 1, 3,… , (2n—1), when it is in the electric field only, similar to the hydrogen atoms; and in the electric field and layer-to-layer interaction, it is split based on 1, 4, … , n2; with the quantum transition, the frequency of the spectrum decreases with the increasing size of the system; apart from a few spectral lines, the intensity of most spectral lines will decreased as the size increases; while the coefficient of spontaneous radiation will increase with the increasing size; the electric field will causethe changes of spectrum frequency; its spectrum frequency shift is proportional to the square of the electric field intensity; apart from a few spectral lines, the frequency shift of spectral lines that is caused by the electric field and layer-to-layer interaction will decrease as the size increases; the interaction will make the level of electronic energy level lower slightly (the order of magnitude is between 10-7—10-9 eV), the slightly increased spectrum intensity and the slightly increased value of coefficient of spontaneous radiation, but it will not influence the frequency of spectrum, intensity, and the trend that coefficient of spontaneous radiation changes with the size; when the size is smaller, the layer-to-layer interaction effect will be significant.
Nanostructured zinc and zinc oxide films were prepared by magnetron sputtering processes and succeeded air annealing treatments. Comparison of reductive degradation rate of methyl orange (MO) by zinc films and photocatalytic degradation rate of MO by zinc oxide films was carried out. Both reductive degradation and photocatalytic degradation process of MO by zinc and zinc oxide films can be described by first order kinetic model. It was found that although MO liquid was most quickly decolorized by metallic zinc films, the mineraliza-tion of MO was not thorough. Observation of extra ultraviolet absorption peaks indicated the formation of aromatic intermediates. On the other hand, although the photocatalytic degradation rate of MO liquid by ZnO films was only as about 1/4 large as the reductive degradation rate by zinc films, no signs of aromatic intermediates were found. Moreover, it was found that partially oxidized zinc oxide film showed higher photocatalytic efficiency than the totally oxidized ZnO films. Synergy effect between zinc and zinc oxide phase in the partially oxidized films was considered to be responsible for the higher photocatalytic efficiency.
Chinese abstract