2006 Vol. 19, No. 2

A crossed molecular beams, state-to-state scattering study was carried out on the F+H2→HF+H reaction at the collision energy of 5.02 kJ/mol, using the highly sensitive H atom Rydberg tagging time-of-flight method. All the peaks in the TOF spectra can be clearly assigned to the ro-vibrational structures of the HF product. The forward scattering of the HF product at v′=3 has been observed. The small forward scattering of the HF product at v′=2 has also been detected. Detailed theoretical analysis is required in order to fully understand the dynamical origin of these forward scattering products at this high collision energy.
A global three dimensional potential energy surface for the F+H2→HF+H reaction has been developed by spline interpolation of about 15,000 symmetry-unique ab initio points, obtained from the multi-reference configuration interaction level with Davidson correction using the aug-cc-pV5Z basis set. In the entrance channel the spin-orbit coupling energy is also included.
Simulations were carried out for studying the periodic phase separation of a symmetric binary polymer blend on the basis of Cahn-Hilliard-Cook theory. The time dependent interaction parameter ?(?) was assumed to undergo a step-wise oscillation. The hierarchic structures composed of both large and small domains were obtained. The mechanism of the periodic formation of hierarchic structures was also demonstrated.
Physical and mathematical models as well as calculation methods of nitrogen bed on porous media have been introduced to evaluate the structural parameters of mesoporous materials. Kelvin's equation is a link between the relative adsorbate pressure, the mean pore radius, and pore capillarity on the basis of macroscopic capillary condensation. However, Kelvin's equation has been identified that it underestimates the calculated pore size of a material especially in the boundary of pore size which is between 2 and 4 nm. Various modifications on Kelvin's equation were mentioned in order to develop a new model to improve the accuracy of pore size calculation. The problems on conventional mathematical models were analyzed and discussed. A number of calculation methods on physisorption and pore size, especially fundamental theories of physisorption, basis of models and their deficiencies are reviewed. It can provide guidance on developing a modified Kelvin's equation for pore size calculation.
Photodissociation dynamics of the CH3 radical at 212.5 nm excitation has been studied experimentally using the H atom Rydberg tagging time-of-flight method. CH3 radicals are produded by photodissociation of CH3I at 266 nm. Translational energy distribution and angular distribution for the CH2 product from CH3 photodissociation at different vibrational levels via the 3s Rydberg state have been measured. From these distributions, product J state distributions are obtained for photodissociation of different vibrationally excited CH3 radicals. The effect of parent vibrational as well as rotational excitation on the dissociation dynamics of CH3 is also investigated in detail. Experimental results in this work show that parent vibrational excitation in the umbrella mode has a significant effect on both rotational excitation and angular distribution of the CH2 product, while parent rotational excitation has obvious effect only on the angular distribution of CH2 product.
The quasiclassical trajectory method is used to study the vector correlations of the reactions Ca+RBr (R=CH3, C2H5 and n-C3H7Br) and the rotational alignment of product CaBr. The product rotational alignment parameters at di?erent collision energies and the vector correlations between the reagent and product are numerically calculated. The vector correlations are described by using the angle distribution functions P(θr),P(φr), P(θr, φr) and the polarization-dependent differential cross sections (PDDCSs). The peak values of P(θr) of the product CaBr from Ca+CH3Br are larger than those from Ca+C2H5Br and Ca+n-C3H7Br. The peak of P(θr) atφr = 3π/2 is apparently stronger than that at φr= π/2 for the three reactions Ca+RBr. The calculation results show that the rotational angular momentum of the product CaBr is not only aligned, but also oriented along the direction which is perpendicular to the scattering plane.The product CaBr molecules are strongly scattered forward. The orientation and alignment of the product angular momentum will affect the scattering direction of the product molecules to varying degrees.
Photodissociation spectra of Ca+-pyridine complex was obtained by reflectron time of flight spectrum (RTOF). Two channels were found from difference photodissociation spectra, one was non-reactive Ca+ cation separation channel, the other one was active channel for product Ca+NH2. Product Ca+ was dominant in the whole region studied and the only product in 530-590 nm region, reactive product Ca+NH2 shared a little present in whole products. Action spectrum as a function of photolysis laser wavelength shows appearance peaks relevant to transitions of complex. Branching ratio supports the information of photodissociation too.
Based on the magnetic interaction energy, using derivative of the magnetic energy density, a model is proposed to compute the magnetic-induced shear modulus of magnetorheological elastomers. Taking into account the influences of particles in the same chain and the particles in all adjacent chains, the traditional magnetic dipole model of the magnetorheological elastomers is modified. The influence of the ratio of the distance etween adjacent chains to the distance between adjacent particles in a chain on the magnetic induced shear odulus is quantitatively studied. When the ratio is large, the multi-chain model is compatible with the single chain model, but when the ratio is small, the difference of the two models is significant and can not be neglected. Making certain the size of the columns and the distance between adjacent columns, after constructing the computational model of BCT structures, the mechanical property of the magnetorheological elastomers composed of columnar structures is analyzed. Results show that, conventional point dipole model has overrated the magnetic-induced shear modulus of the magnetorheological elastomers. From the point of increasing the magnetic-induced shear modulus, when the particle volume fraction is small, the chain-like structure exhibits better result than the columnar structure, but when the particle volume fraction is large,the columnar structure will be better.
Fluidized bed biomass gasifiers can be employed to produce hydrogen-rich gas. A non-premixed combustion model is used for biomass air-steam gasification in the gasifier, and the simulations were carried out by using the FLUENT 6.0 software. The simulation results are compared with the experimental data. The effects of the steam to biomass ratio (S/B), the equivalence ratio (ER), and the size of biomass particles on the hydrogen yield were studied. Meanwhile, the distributions of hydrogen inside the gasifier at different conditions are also described.
The adsorption and the growth of ZnO on α-Al2O3(0001) surface at various temperatures were theoretically calculated by using a plane wave pseudopotentials (USP) method based on density functional theory.The average adsorption energy of ZnO at 400, 600 and 800 ℃ is 4.16±0.08, 4.25±0.11 and 4.05±0.23 eV respectively. Temperature has a remarkable effect on the structure of the surface and the interface of ZnO/α-Al2O3(0001). It is found that the Zn-hexagonal symmetry deflexion does not appear during the adsorption growth of ZnO at 400 ℃, and that the ZnO[10-10] is parallel with the [10-10] of the α-Al2O3(0001), which is favorable for forming ZnO film with the Zn-terminated surface. It is observed from simulation that there are two kinds of surface structures in the adsorption of ZnO at 600 ℃: one is the ZnO surface that has the Zn-terminated structure, and whose [10-10] parallels the [10-10] of the substrate surface, and the other is the ZnO[10-10] //sapphire [11-10] with the O-terminated surface. The energy barrier of the phase transition between these two different surface structures is about 1.6 eV, and the latter is more stable. Therefore,the suitable temperature for the thin film growth of ZnO on sapphire is about 600 ℃, and it facilitates the formation of wurtzite structure containing Zn-O-Zn-O-Zn-O double-layers as a growth unit-cell. At 600 ℃, the average bond length of Zn-O is 0.190±0.01 nm, and the ELF value indicates that the bond of (substrate)-O-Zn-O has a distinct covalent character, whereas the (Zn)O-Al (substrate) shows a clear character of ionic bond. However, at a temperature of 800 ℃, the dissociation of Al and O atoms on the surface of the α-Al2O3(0001) leads to a disordered surface and interface structure. Thus, the Zn-hexagonal symmetry structure of the ZnO film is not observed under this condition
Density functional theory (DFT) was used to calculate molecular descriptors (properties) for 12 fluoro-quinolone with anti-S.pneumoniae activity. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) were employed to reduce dimensionality and investigate in which variables should be more effective for classifying fluoroquinolones according to their degree of an-S.pneumoniae activity. The PCA results showed that the variables ELUMO, Q3, Q5, QA, logP, MR, VOL and △EHL of these compounds were responsible for the anti-S.pneumoniae activity. The HCA results were similar to those obtained with PCA.The methodologies of PCA and HCA provide a reliable rule for classifying new fluoroquinolones with antiS.pneumoniae activity. By using the chemometric results, 6 synthetic compounds were analyzed through the PCA and HCA and two of them are proposed as active molecules with anti-S.pneumoniae, which is consistent with the results of clinic experiments.
Density functional method (B3p86) was used to optimize the structure of the molecule Fe2. The result showed that the ground electronic state for the molecule Fe2 is nonet state instead of septet state, which indicates that there is a spin polarization effect in the molecule Fe2, i.e., in which there are 8 parallel spin electrons.In this case, the number of the unpaired d-orbit electrons is the largest, and these electrons occupy different spatial orbitals so that the energy of the molecule Fe2 is minimized. Meanwhile, the spin pollution was not found because the wave functions of the ground state do not mix with those of the higher energy states. In addition, the Murrell-Sorbie potential functions with the parameters for the ground electronic state and other exited electronic states of the molecule Fe2 were derived. The dissociation energy, equilibrium bond length and the vibration frequency for the ground electronic state of the molecule Fe2 are 3.5522 eV, 0.2137 nm and 292.914 cm-1, respectively. Its force constants f2, f3 and f4 are 1.4115×102 a J/nm2, -37.1751×103aJ/nm3 and 98.7596× 104 a J/nm4, respectively. The other spectroscopic parameters ωexe, Be and αe for the ground electronic state of Fe2 are 0.3522, 0.0345 and 0.4963× 10-4 cm-1, respectively.
In situ thickness dependent photoluminescence (PL) measurements of tris(8-hydroxyquinoline) aluminum(Alq3) film were performed. At the beginning of Alq3 deposition on the glass substrate, the Alq3 emission showed a sharp red-shift. Further deposition of Alq3 resulted slight red-shift, and finally tended to saturated value. The total red-shift of about 12 nm was observed for the Alq3 film thickness range from 2 to 500 nm.This red-shift was attributed to the change from the 2D to 3D exciton state with increasing Alq3 film thickness. Meanwhile, the PL intensity of Alq3 emission increased continuously, and showed a rate change at the initial deposition of Alq3 due to non-rediative decay of excitons arised from the interaction between excitons and the substrate, and finally tended to saturation with the Alq3 thickness.
By using the plane-wave-expansion method, the band structure of three-dimension phononic crystals was calculated, in which the cuboid scatterers were arranged in a host with a face-centered-cubic (FCC) structure.The influences of a few factors such as the component materials, the filling fraction of scatterers and the ratio (RHL) of the scatterer's height to its length on the band-gaps of phononic crystals were investigated.It is found that in the three-dimension solid phononic crystals with FCC structure, the optimum case to obtain band-gaps is to embed high-velocity and high-density scatterers in a low-velocity and low-density host. The maximum value of band-gap can be obtained when the filling fraction is in the middle value. It is also found that the symmetry of the scatterers strongly influences the band-gaps. For RHL>1, the width of the band-gap decreases as RHL increases. On the contrary, the width of the band-gap increases with the increase of RHL when RHL is smaller than 1.
The removal of Ni ion from an aqueous solution was carried out by solvent sublation of Ni-diacetyldioximesodium dodecylbenzensulphonic (sublate) into isopentanol. The ratio of surfactant to Ni-diacetyldioxime complex at 20:1 was most effective for the removal, with over 90% Ni ion removed from the aqueous solution within 1 h. The effects of electrolytes (e.g. NaCl), non-hydrophobic organics (e.g. ethanol) and pH of the solution upon the process were well studied. The removal rate was enhanced by higher airflow rates but almost independent on the volume of the organic solvent floating on the top of the aqueous column. The process of solvent sublation followed first order kinetics. A characteristic parameter, the apparent activation energy of attachment of the sublate to bubbles, was estimated to be 8.99 kJ/mol. Furthermore, the simulation of a mathematical model with the experiment data on the solvent sublation of Ni-diacetyldioxime-SDS was proved to be validated.
The cadmium(Ⅱ)-glycine system was studied by the two experimental techniques, ion sensitive electrode (ISE) and differential pulse polarography (DPP), and the experimental data obtained were used by a unified mathematical treatment to calculate the complex stability constants. The combination of the two techniques is of many advantages as ISE can be performed at low [LT]:[MT] ratios and significantly higher [MT], whereas DPP could be used well at large [LT]:[MT] ratios and much smaller [MT]. This makes it possible to study a metal-ligand system in a relatively broader range of experimental conditions that, in turn, provides more information about the metakligand system of interest. Applying the unified mathematical treatment to the cadmium-glycine system, two new complexes MHL and ML2(OH) as well as three complexes ML, ML2 and ML3, reported in literatures, could be modeled and all their stability constants have been refined.
Annealing study of the Al/GaSb system was performed by using a slow positron beam and the measurement of X-ray diffraction. The S parameter against positron energy data were fitted by a three layer model (Al/interface/GaSb). It was found there was a ~5 nm interfacial at the region between the Al layer and bulk in the sample of as-deposited. After the 400 ℃ annealing, this interfacial region extends to over 40 nm and S parameter dramatically drops. This is possibly due to a new phase formation induced by the atoms'inter-diffusion at the interface. The annealing out of the open volume defects in the Al layer was revealed by the decrease of the S parameter and the increase of the effective diffusion length of the Al layer. Annealing behaviors of Sb and Lb of the GaSb bulk showed the annealing out of positron traps at 250 ℃. However,further annealing at 400 ℃ induces formation of positron traps, which are possibly another kind of VGarelated defect and the positron shallow trap GaSb anti-site. The results of the X-ray diffraction experiment verified the conclusion of obtained by using positron technology.
By measuring M-T curves, ρ-T curves and MR-T curves of the samples under different temperatures, the influence of Dy doping (0.00 ≤ x ≤0.30) on the magnetic and electric properties of La0.7-xDyxSr0.3MnO3 has been studied. The experimental results show that, with the increase of the Dy content, the system undergoes a transition from long range ferromagnetic order to the cluster-spin glass state and further to antiferromagnetic order. For the samples with x=0.20 and 0.30, their magnetic behaviors are abnormal at low temperature, and their resistivities at low temperature have a minimum value. These peculiar phenomena not only come from the lattice effect induced by doping, but also from extra magnetic coupling induced by doping.
The coordination reactions of Cu(Ⅱ) and Ni(Ⅱ) with acid alizarine blue B (AABB) in the presence of cetyltrimethylammonium bromide (CTAB) micelle were investigated using the microsurface adsorptionspectral correction technique (MSASC). The aggregation of AABB on CTAB followed the Langmuir isothermal adsorption law. The enrichment of AABB on CTAB sensitized the complexation between Cu(Ⅱ) or Ni(Ⅱ)and AABB. The binding ratio of AABB to CTAB was 1:2.5, and monomeric aggregate, AABB2CTAB5, was formed with an adsorption constant of 5.95×105 at 20 ℃ or 2.48×105 at 40 ℃. In the ternary complexation, the ratio of AABB:Cu and AABB:Ni were 1:1 and 1:2.5, respectively. Two types of aggregates, Cu2.AABB2·CTAB80 and Ni5.AABB2.CTAB80, were formed.
A novel materials design procedure based on the co-doping of metal nanoparticle and azo dye compound (MNPADC) is developed to improve the properties of functional molecules. The synthesized materials were characterized by transmission electron micrograph (TEM), ultraviolet-visible absorption spectra (UV-Vis) and fluorescence spectra (FS). It was found that the fluorescence intensity of methyl orange (MO) was enhanced by 5 times in the aqueous composite system doped with silver nanoparticles whereas it was reduced by 15% and 20% in composite films with co-mixing and coating structures, respectively. The results indicate that the properties of functional molecules can be greatly improved in composite film with supra molecular structure and that the procedure presented here is effective.