2006 Vol. 19, No. 4

Theoretical studies of F atom reaction with trans-1,3-butadiene were carried out at the CCSD(T)/6-311G(d,p)/B3LYP/6-311G(d,p) levels. Energies and structures for all reactants, products and transition states were determined. Two reaction pathways involving the formation of the complexes CH2CHCHFCH2 and CH2CHCHCH2F were found in this reaction. Theoretical results suggest that the H atom channel observed in previous crossed beam experiment occurs likely via these two long-lived complex formation pathways. For the complex CH2CHCHFCH2 pathway, another reaction channel (C2H3+C2H3F) is also accessible. Relative importance of the C2H3+C2H3F channel versus the H formation channel via the same reaction pathway has also been estimated, suggesting that it would be difficult to observe the C2H3+C2H3F channel in a crossed molecular beam experiment. Theoretical analysis also shows that the HF formation proceeds via direct abstraction mechanisms, though it is likely a minor process in this reaction.
A modified molecular structural mechanics method, based on molecular mechanics and similar to the finite element method, was developed. The energy of a system was expressed by the force field functions of the molecular mechanics. Under the small deformation assumption and by the principle of minimum potential energy, the system function was established. The properties of tension and bending of single-walled carbon nanotubes were analyzed. The Young's modulus is about 0.36 TPa nm, which agrees perfectly with the results of previous analysis by other researchers. It is found, for the first time, that the Young's moduli, for Zigzag nanotubes, are different from each other when the system energy was expressed as the sum of two or three individual energy terms in molecular mechanics. Whereas, the Young's moduli were the same for the Armchair nanotubes. It is found, when simulating the bending, that the deflections are closer to the theoretical ones, of the classical elasticity, when the diameter of the carbon nanotube increases.
The microstructure of diamond films was studied by slow positron beam and Raman spectroscopy. For the Raman spectroscopy experiment on diamond films, a high fraction of the sp3 hybridized bond was detected in samples. Positron annihilation spectra analysis further illuminated that the concentration and types of defects were different in each sample. S-E curves of all samples showed that diamond crystal structures had obvious variation in each sample. These results indicated that positron annihilation spectroscopy was an effective means to measure microstructure of diamond films.
Tensile deformation behaviors and the Poisson's ratio of single-walled carbon nanotubes (SWCNTs) are numerically studied, using the molecular dynamics (MD) method. Effects of several structural features of crystal cells of SWCNTs, i.e., the size, chirality and strain, on their mechanical properties are analyzed systematically. The simulations indicate that Armchair SWCNTs (8, 8)-(22, 22) and Zigzag SWCNTs (9,0)-(29,0) can be stretched by 35%-38% and 20%-27% without sign of plasticity, respectively. The Young's modulus of SWCNTs under tension ranges from 960 GPa to 750 GPa as their radii increase. The Young's modulus of zigzag SWCNTs is higher than that of armchair SWCNTs. Additionally, three SWCNTs (9,9),(12,6) and (16,0) are investigated to obtain their Poisson's ratio under tensile and compressive loading. The results show that the Poisson's ratio of nanotubes decreases generally as the strain increases. Under the same tensile strain, the Poisson's ratio decreases as the chiral angles of SWCNTs decrease, while their Poisson's ratios increase under the same compressive strain.
Twenty-tow possible isomers for C76BN were studied by INDO methods. The two most stable geometries are 52,53-C76BN and 29,28-C76BN, in which boron and nitrogen atoms are connected with each other and located at the 6/6 bond near the longest axis of C78(C2v). Electronic spectra of C76BN were investigated with INDO/SCI method. UV absorptions of C76BN are red-shifted compared with those of C78(C2v). The structures and IR spectra for the four stable isomers of C76BN were calculated by AM1 method. It was indicated that the substitution of the BN unit weakens the conjugation of carbon atoms, leading to the decrease of IR frequencies.
To expose the statistical properties of the degenerated spectrum, with the aid of the random matrix theory,a possible form of the NNS distribution function of the degenerate spectrum was proposed by providing a solution in terms of the same-degeneracy case. The results indicate that the target spectrum is transformed into two sub-spectra: a random one and a regular one, and that the repulsion level of the regular spectrum is also decreased.
The melting curve of MgSiO3 perovskite was simulated using molecular dynamics method combining with the effective pair potentials under the lower mantle conditions. It was shown that the state equation simulated for MgSiO3 perovskite is very successful in reproducing accurately the experimental data over a wide range of pressure. The pressure dependence of the simulated melting temperature of MgSiO3 perovskite is in agreement with the recent experimental data. The melting curve simulated for MgSiO3 is very steep at pressures below 60 GPa first, then it becomes smooth with increasing pressure. At the core mantle boundary pressure 135 GPa, MgSiO3 perovskite melts at 6500 K, which is significantly lower than that of the extrapolations of the experimental data from Zerr and Boehler.
Molecular dynamics simulation was used to study the melting of MgO at high pressures. The melting temperature of MgO was accurately obtained at elevated temperature and high pressure after corrections based on the modern theory of melting. The calculated melting curve was compared with the available experimental data and other theoretical results at the pressure range of 0-135 GPa. The corrected melting temperature of MgO is in good agreement with the results from Lindemann melting equation and the twophase simulated results below 15 GPa.
A theoretical method was proposed to extend a bridge density functional approximation (BDFA) for the non-uniform hard sphere fluid to the non-uniform Lennard-Jones (L J) fluid. The DFT approach for LJ fluid is simple, quantitatively accurate in a wide range of coexistence phase and external field parameters.Especially, the DFT approach only needs a second order direct correlation function (DCF) of the coexistence bulk fluid as input, and is therefore applicable to the subcritical temperature region. The present theoretical method can be regarded as a non-uniform counterpart of the thermodynamic perturbation theory, in which it is not at the level of the free energy but at the level of the second order DCF.
The electromotive force (e.m.f.) of solid oxide fuel cells using biomass produced gas (BPG) as the fuels is calculated at 700-1,200 K using an in-house computer program, based on thermodynamic equilibrium analysis. Tour program also predicts the concentration of oxygen in the fuel chamber as well as the concentration of equilibrium species such as H2, CO, CO2 and CH4. Compared with using hydrogen as a fuel, the e.m.f.for cells using BPG as the fuels is relative low and strongly influenced by carbon deposition. To remove carbon deposition, the optimum amount of H2O to add is determined at various operating temperatures.Further the e.m.f, for cells based on yttria stabilized zirconia and doped ceria as electrolytes are compared.The study reveals that when using BPG as fuel, the depression of e.m.f, for a SOFC using doped ceria as electrolyte is relatively small when compared with that using Yttria stabilized zirconia.
Two series monotailed porphyrins, Cobalt-5-{4-[ω-(1-adamantaneamino) alkyloxy]phenyl}-10,15,20-triphenyl porphyrinate (CoPCnA, n=4,5,6) anj Nickel-5-{4-[ω-(1-adamantaneamino)alkyloxy]phenyl}-10,15,20-triphenyl porphyrinate (NiPCnA, n=4,5,6), were synthesized, in which the porphyrin moiety was connected to 1-adamantanamine via a flexible hydrocarbon chain. The fluorescence quenching between these donor substrates and mono-6-p-nitrobenzoyl-β-cyclodextrin (NBCD) was studied in detail. Distinct fluorescence quenching occured in these supramolecular systems. This quenching was attributed to the photoinduced electron transfer (PET) inside the supramolecular assembly between the porphyrin donors and cyclodextrin acceptors. Detailed Stern-Volmer constants were measured and they were partitioned into dynamic SternVolmer quenching constants and static binding constants. It was demonstrated that the PET interaction between the porphyrin subunits and NBCD is indeed effective.
Using ethylene glycol as solvent and reductant, CuCl2·2H2O, (NH2)2CS and self-prepared GaCl3 as the starting materials, CuGaS2 nanostrucutures were synthesized on a large scale at 220 ℃. Powder X-ray diffraction,transmission electron microscopy, field-emission scanning electron microscope, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy were used to characterize the products. It demonstrated the evolution of the CuGaS2 particles from spherical assemblies to flowerlike morphology, over time,at 220 ℃. Simultaneously, we elucidated the specific roles of reaction temperature, reaction time and solvent in the formation of the final CuGaS2 nanostructures. A possible formation mechanism of CuGaS2 nanostrucutures was also discussed. The room temperature photoluminescence spectrum showed blue-shift and an increase of intensity, with a decrease in the sizes of CuGaS2 particles.
A kind of ruthenium oxide with smaller particles and higher porosity was prepared by a sol-gel process with RuCl3·xH2O and NaHCO3 solution. Several details concerning this new material, including crystal structure,particle size as functions of the temperature, and electrochemical properties were also reported. The optimal annealing temperature was 210 ℃ and the powder annealed at this temperature had a rate capacitance of 541 F/g. In addition, the rate capacitance of the composite electrode reached 802 F/g after 10% carbon black was added, much higher than any previously reported value. High energy density supercapacitors were built with the newly discovered electrode material. Energy densities as high as 67 J/g were obtained based on the RuO2 ·xH2O alone. By introducing the highly porous carbon black into the electrode, energy densities great than 100 J/g could be achieved. The power density of the capacitor was enhanced significantly.
The perovskite-type-oxide solid solution Ba0.97Ce0.8Ho0.2O3-α was prepared by high temperature solidstate reaction and its single-phase character was confirmed by X-ray diffraction. The ionic conduction of the sample was investigated using electrical methods at elevated temperatures, and the performance of the hydrogen-air fuel cell using the sample as solid electrolyte was measured, which were compared with those of BaCe0.8Ho0.2O3 - α. In wet hydrogen, BaCe0.8 Ho0.2 O3 - α almost exhibits pure protonic conduction at 600-1000 ℃, and its protonic transport number is 1 at 600-900 ℃ and 0.99 at 1000 ℃. Similarly,Ba0.97Ce0.8Ho0.2O3-α exhibits pure protonic conduction with the protonic transport number of 1 at 600-700 ℃, but its protonic conduction is slightly lower than that of BaCe0.8Ho0.2O3-α, and the protonic transport number are 0.99-0.96 at 800-1000 ℃. In wet air, the two samples both show low protonic and oxide ionic conduction. For Ba0.97Ce0.8Ho0.2O3-α, the protonic and oxide ionic transport numbers are 0.01-0.11 and 0.30-0.31 respectively, and for BaCe0.8Ho0.2O3-α, 0.01-0.09 and 0.27-0.33 respectively. Ionic conductivities of Ba0.97Ce0.8Ho0.2O3-α are higher than those of BaCe0.8Ho0.2O3-α under wet hydrogen and wet air. The performance of the fuel cell using Ba0.97Ce0.8Ho0.2O3-α as solid electrolyte is better than that of BaCe0.8Ho0.2O3-α. At 1000 ℃, its maximum short-circuit current density and power output density are 465 mA/cm2 and 112 mW/cm2, respectively.
An effective procedure was demonstrated to arrange spherical micro-beads into ordered, long, line-shape arrays by means of "micromolding in capillaries" in soft lithography. Polystyrene (PS) micro-beads with 2-3 mm of diameter were used as units and arranged by molding in continuous micro-channels formed by the conformal contact between a glass substrate and an elastomeric stamp with micrometer-scale line patterns on the surface. An aqueous emulsion of PS micro-beads filled these channels by capillary action and was allowed to solidify. The stamp was then removed. The PS micro-beads could be assembled into a string of long line-shape arrays, and the strings were then joined by heating them to their softening temperature.In order to separate the PS micro-bead string from the substrate, the glass was covered with a thin layer of Al or polymethyl methacrylate. After the Al layer was dissolved, the string of PS micro-beads would be released. A string of micrometer scale PS beads can be used as a simple and direct "model" of a real macromolecular chain. It is hopeful to show an analogue with the condensed process of real macromolecules in a mesoscopic scale using the "string of PS micro-beads".
Different titanium oxide powders (ATiO2, BTiO2) were pretreated in ammonia (NH3) gas at high temperatures. After the pretreatment, the color of the titanium oxide powders changed from white to yellow or gray depending on the pretreatment temperatures. Morphologies and structures of the treated titanium oxide powders were characterized by physical chemical methods. XRD measurements showed that the crystalline structures were mainly mixture of anatase and rutile for the ATiO2 but only anatase for the BTiO2. Stronger absorption of visible light was observed for both types of samples using UV-Vis diffuse reflectance spectra.X-ray photoelectron spectroscopy demonstrated that doped nitrogen existed on the surface TiO2 after ammonia gas pretreatment. The photocatalytic activities of the treated titanium oxide samples were evaluated via the photodegradation of methyl orange and phenol in aqueous suspensions. No obvious improvement in photocatalytic activity was achieved by ammonia pretreatment although it could enhance the absorption of light. Effects of treatment temperatures on photoactivities were complete different for ATiO2 and BTiO2 (i.e. higher treated temperatures yielded higher activities for BTiO2 but lower for ATiO2). All samples yielded lower activity levels after ammonia pretreatment without regard to pretreatment temperature or the reaction light resource.
Sliver nanoplates were prepared through a visible light induced reduction process by a reaction between sodium citrate and silver nitrate in an aqueous solvent at room temperature. UV-Vis spectra were employed to monitor the growth of the silver nanoplates. The resulting spectra indicated that, at an early stage,the products were spherical particles with planar nanoparticles appearing and growing subsequently. In the last stages of the process, some spherical particles were consumed by the growth of the nanoparticles,through an Ostwald ripening mechanism. Furthermore, it was found that the addition of either Poly(Vinyl Pyrrolidone) (PVP) or excessive citrate could stabilize the colloidal system effectively, and that rigorous stirring was necessary for the anticipant products. Introduction of a large quantities of sodium hydroxide can dramatically accelerate the reactive rate of the photoreduction process.
(Ca, Mn)-codoped Ba1-xSrxTiO3 (BST) solid solution, i.e. Ba0.4Sr0.5Ca0.08Mn0.02TiO3, was successfully synthesized via sol-gel process. The product was characterized by TG-DTA thermal analyses, XRD, TEM.The effects of both curing temperature and applied voltage on the resistance, etc. were investigated. It showed that the structure of BST was unable to be changed even though it was codoped by Ca2+ and Mn2+. TEM photographs demonstrated the influence of curing temperature on the morphologies of the tested samples. The dependence of resistance on the curing temperature illustrated that (Ca, Mn)-codoped BST was capable of exhibiting the positive temperature coefficient (PTC) effect at low frequency; nevertheless,it might display the negative temperature coefficient (NTC) effect at other frequencies. The relationships between the resistance and applied voltage revealed that the resistance property of (Ca, Mn)-codoped BST appeared at low frequencies, but its property of capacitive reactance might present at high frequency. These findings mean that the electrical property of BST can be adjusted by codoping method. These phenomena can be explained by the grain boundary resistance effect, Heywang model and ion polarization theory.