2005 Vol. 18, No. 6

All the microscopic and dynamic information of a chemical change from the reactant to the product can be obtained using the laser and crossed molecular beam techniques. They can yield many interesting physical measurements such as differential reaction cross section, integral reaction cross section, excitation function, quantum state distribution and et al. Based on this, the chemical reaction kinetics were developed from the macroscopic to the microscopic elementary state-to-state level. Quantum mechanical reactive scattering theories can give the most complete description of all elementary state-to-state bimolecular reactions allowed by natural law. In this review, several current quantum mechanical reactive scattering methods, such as time-dependent wave packet propagation, closed-coupling differential equation, the S-matrix variational approach and a linear combination of arrangement channels-scattering wavefunction and their applications are given. In addition, further development of the aforementioned theories is also explored.
Strong backward first Stokes (BS) in H2 is observed when a single longitudinal mode fundamental frequency Nd:YAG laser (1.06 μm, pulsed width about 9 ns, linewidth 0.003 cm-1) is used as the pump source. Using a pump energy of 120 mJ, photon conversion efficiency of FS and BS was determmed to be 66% and 15% respectively in 1.5 MPa H2, while in 4.0 MPa H2 the respective values are 46% and 39%. Due to their propagation in opposite directions, there is tension between FS and BS, which leads to a relaxation of the oscillation that splits both FS and BS pulses into two peaks, with the BS pulses being narrowed to about 1 ns. Surprisingly, the BS peak power reaches twice that of the pump, which can never happen in the FS case. Furthermore, the beam quality of BS is much better than that of both FS and pump. At 4 MPa of H2 pressure and a 10 Hz cycle rate, the thermal release of the Raman process deteriorates the FS beam quality, without noticeably affecting that of BS. According to this calculations, within the present experimental conditions, the stimulated Raman scattering process does not reach the steady state. Because of this, all of the experimental results can be explained explained by a related transient state, theory of stimulated Raman scattering.
A high resolution study of the high-n Rydberg H atom scattering with helium was carried out using the H atom Rydberg tagging time-of-flight technique. Differential cross sections were measured for scattering process of H(n)+He→H(n′)+He at the collision energy of 0.526 eV. Experimental result indicates that the scattered H(n′) product is mainly forward distributed, with signals observed in the wide range of angles at the sideway and forward scattering directions. At the sideway and forward directions, a lot of oscillatory structures in the angular distributions are present. Detailed analysis also shows that the principle quantum number, n, is not changed much for the Rydberg H atom at the forward scattering direction. This work provides a good test ground to investigate theoretically the exact collision dynamics between the high-n Rydberg H atom and the helium atom.
Photoionization studies of chlorobenzene were performed by using a time-of-flight mass spectrometer (TOF-MS) with vacuum ultraviolet (VUV) photons from the Heifei synchrotron radiation source. The photoionization mass spectrum and the photoionization efficiency (PIE) curves of both parent and fragment ions were measured. The appearance potentials of the major ions were obtained from their PIE curves. From these data, the standard formation enthalpies of C6H5Cl+, C6H+5 and C4H+3 were evaluated, some dissociative energy was derived. We will be able to detect chlorobenzen with SPI-TOFMS and 118.0 nm laser light.
A low-pressure premixed gasoline/oxygen/argon flame was studied by using molecular-beam sampling mass spectrometry combined with a tunable synchrotron radiation photoionization technique. The photoionization time-of-flight mass spectrum of gasoline/oxygen/argon in the flame was recorded and the ionization energies of some species were detected. Compared with the ionization energies in literatures, the isomers were uniquely identified. The reaction process of five typical hazardous products was empirically analyzed by species concentration profiles. The experimental results are helpful in establishing the kinetic modeling for a gasoline/oxygen flame.
The A2Πu-X2Πg electronic absorption spectrum of the Cl2+ molecular cation in the region between 16820 and 17350 cm-1 was observed by employing optical heterodyne magnetic rotation enhanced velocity modulation spectroscopy. Cl2+ is a paramagnetic molecule; however, the intensities of some spectral lines, belonging to three bands whose origins are near 17282, 17324 and 16913 cm-1, respectively, remain unchanged with in the magnetic field. This indicates that both the upper and lower states have a weak Zeeman effect. The Zeeman contribution is nearly zero for the 2Π1/2 state, while nonvanishing for the 2Π3/2 state. Therefore, this behavior for the spectral assignment of Cl2+, including its isotopics was utilized and the identity of these bands was confirmed as members of the Ω=1/2 component of the electronic transition conveniently and unambiguously. The assigned bands are the (3, 7) band of the Ω=1/2 component of 35Cl+2 and 35Cl37Cl+ and the (2, 7) band of the Ω=1/2 component of 35Cl2+. It extends the range of vibrational assignments considerably in both the ground and the excited state, and leads to the successful rotational analysis. New molecular constants of Cl2+ were obtained from the observed line positions, band by band, using a weighted leastsquares fitting procedure.
A new method for producing electronically excited nitrogen monohalides NX(b) (X=F,Cl,Br) is reported. The strong emission spectra of NBr(b1Σ+→X3Σ–) are observed when alkyl bromides (CHBr3, CH2Br2, C2H5Br, and C4H9Br) are added to a stream of active nitrogen, generated by a hollow-cathode discharge of N2, in a flowing afterglow system. Some tentative experiments show that the electronically excited NBr(b) is formed by means of metastable N2(A3Σu+) Electronic-to-Electronic energy transfer to NBr(X), which is from the reaction of N(4S) with alkyl bromides. The emission spectra of NCl(b1Σ+→X3Σ–) are obtained when CCl4 or SOCl2 is admitted into a flow of active nitrogen, but neither CHCl3 nor CH2Cl2 addition results in such an emission. It has been proposed that the origin of the excited NCl(b) is an energy transfer from N2 (A) to NCl(X), generated by the reaction of N(4S) with CCl3 (or SOCl2). Similar experiments are also carried out with SF6 as reagent of active nitrogen, or as mixture with N2 in the discharge. By recording fluorescence it was found that excited NF(b) is produced only under discharge through N2/SF6 mixture. The NF(b) state presumably arises from the energy transfer from N2(A) to NF(X), and the latter is generated from the abstraction of fluorine by N(4S) from SF5.
Positron annihilation lifetime spectroscope(PALS) was applied to investigate the micro-structural changes of polyethylene(PE) which was irradiated by γ-ray or ultraviolet radiation, the spectra were decomposed into three lifetime components using PATFIT package. Then it was found that the shifts of the degree of cross linking and crystallinity were detected effectively in samples. Moreover, a small quantity of oxygen, which involved in the crosslinking process, was measured sensitively by PALS. The regularity of positron lifetime intensity vs radiation intensity in γ irradiated sample was opposite to that in ultraviolet irradiated one, which is due to the preparation methods of samples and the change of polar functional group in initiator. Furthermore, contrastive patterns were studied by positron doppler broaden(DB) method and the results were agreed well with PALS data mentioned above.
To study electron affinity kinetics, a shock tube method was applied, in which the test gas was ionized by a reflected shock wave and subsequently quenched by a strong rarefaction wave. As the quenching speed of 106 K/s was reached, a nonequilibrium ionizationrecombination process occurred, which was dominated by ion recombination with electrons. A Langmuir electrostatic probe was used to monitor variation in the ion number density at the reflection shock region. The working state of the probe was analyzed, and a correction was introduced for reduction of the probe current due to elastic scattering in the probe sheath. The threebody electron affinity rate coefficient of the fluorine atom over the temperature range 1200 to 2200 K in an ambiance of argon gas was directly determined. The temperature dependence of electron affinity rate coefficient was discussed.
In order to study the quantum reaction dynamics of large molecular systems, the timedependent quantum wave packet approach was used to study the F+CD4→CD3+DF reaction systems. The semirigid vibrating rotor model proposed by J.Z.H. Zhang was used on the MJ1 potential energy surface. The barrier height of the MJ1 PES was about 66 meV. In the semirigid vibrating rotor model, the fragment CD3 was fixed to in the geometry, its transition state value, because from the reactant to the transition state the C-D bond in the CD3 group almost remains constant, which can be treated as a spectator bond. The numerical calculation showed that there were oscillatory structures in the energy dependence of the calculated integral cross section. Those structures are generally associated with dynamic resonances. Cross section and rate constant were calculated based on the MJ1 PES of the ground state. These results are comparable to the results of previous calculations and reaction dynamic experiment results. At low temperature and collision energies, the tunneling effect works most remarkably in the reaction process to make the D abstraction easier. At high temperatures and collision energies, the rate constant is higher than the experimental results.
The reaction of N(4S)+CH3X(X=Cl、Br) was studied by the ab initio method. The geometries of the reactants, transition states and products were optimized at the MP2/6-311+G(d,p) level. The corresponding vibration frequencies were calculated at the same level. The single-point calculations for all the stationary points were carried out at the MP2/6-311++G(3df,2p) and the QCISD(T)/6-311+G(d,p) levels using the MP2/6-311+G(d,p) optimized geometries. The energies of all the stationary points were calculated by the G2MP2 method. The results of this theoretical study indicate that the reaction has three reaction channels: H abstraction reaction channel a, Cl or Br abstraction reaction channel b and substitution reaction channel c. For the N(4S)+CH3Cl reaction, reaction channel a is the main reaction channel. Reaction channels b and c may have a slight contribution in the reaction. For the N(4S)+CH3Br reaction, reaction channel a is the main reaction channel. Reaction channels b and c may have some contribution in the reaction.
The mechanisms of the cycloaddition reaction of singlet GeX2(X=F,Cl) with formaldehyde was studied employing the HF/6-311+G theory. The electron-correlation corrections have been further considered by the fourth-order Muller-Plesset perturbation theory (MP4SDTQ/6-311+G). The results show that this reaction proceeds in two steps: ① Difluorogemylene and formaldehyde form an intermediate complex, which is a barrierless exothermal reaction; ② the intermediate complex isomerizes to form the product, which is a rate-control step in the whole reaction. In the second step, the calculated barrier heights are 216.7 and 196.4 kJ/mol before and after considering electron-correlation effects. Compared with that of the cycloaddition reaction of difluorosilylene with formaldehyde, the cycloaddition reaction of difluorogemylene with formaldehyde is relatively slow, whereas the cycloaddition reaction of dichlorogemylene with formaldehyde can be comparable in speed.
Using the -CHR-(CH2)3-NFCH3(R=H, CH3, CH2CF3, CHO, COCH3) as the computational model, the two possible intramolecular reactions, nucleophilic substitution on nitrogen and elimination reaction, were studied at the theoretical level of MP2(full)/6-31+G(d,p). The results indicate that the elimination mechanism, when the -CHR radical is more basic (R=H, CH3, CH2CF3) leading to linear products R-CH2-(CH2)3N=CH2 is preferred. In contrast, electro-withdrawing groups CHO and COCH3 on the attacking site will favor the intramolecular nucleophilic substitution of nitrogen and form 5-membered heterocyclic compounds. These theoretical predictions agree with the available experiments.
Geometries of 5-hydroxy-7, 4′-dimethoxyflavanone abtained from Artemisia Ordosica Kraschen were calculated theoretically by both ab initio (Hartree-Fock) and density functional theory(B3LYP). The 1H and 13C-NMR of the compounds were also calculated using the GIAO (gauge-independent atomic orbital)method. Statistical error analysis for the theoretically predicted δH and δC values versus those experimentally observed for the compounds was discussed. The results show that the atom H at C(2) is β-H, so the absolute configuration of the compound is the S conformer.
The simplest organic light-emitting-diode (OLED) device is a two layer device of: ITO/HTL/ETL/Mg: Ag, in which HTL or ETL can act as light emitter. The mobilities of charge are important in optimizing the performance of OLED devices, as high mobilities reduce the resistance of the device leading to greater power efficiency. The electron-transport in the organic solid can be viewed as an electron hopping process. By means of DFT (B3LYP) methods, the structures of two kinds of electron-transport materials in neutral, cationic and anionic states were optimized. The results suggest that the process of electronic transmission of 2,5-diphenyl-1,3,4-oxadiazole is mainly the N→O transferences, the process of electronic transmission of 3,4,5-triphenyl-1,2,4-triazole is mainly the N(double linkage)→N(single linkage) transferences and the transition from the triazole ring to the benzene ring connected with the N atom. The third position of the benzene ring was substituted by the electron acceptor groups, the electronic transmission performance was enhanced, while it was substituted by the electron donor groups, the electronic transmission performance was reduced.
The electronic structures, geometric structures and some molecular properties (generalized structural indexes) of quinazoline derivatives were computed by using density functional theory and molecular mechanism methods to investigate the quantitative structure-activity relationship (QSAR) of the inhibitory activity toward the nuclear factor kappa B. Via a stepwise regression analysis, some main factors affecting the activity of the compounds were factored out, and then the QSAR equation was effectively established. It was found that the hydrophobic parameter of the substituent on ring D is the main factor affecting the inhibitory activity of the compound. The analysis indicated, the larger the hydrophobic parameter, the higher the inhibitory activity of the compound. In addition, the net charge of the first atom and the stereoscopic parameter (MR1) of the substituent R1 on A-ring as well as the net charge of C3 are closely correlated with the inhibitory activity of the compound. In order to test the predicted results of the QSAR equation, we adopted the “leave one out” cross-validation , and found that the calculated coefficient q2 was rather high and the predicted results were both accurate and reliable. Such facts show that the obtained equation has great predictive ability. The above results can offer an important theoretical guide in the search for new quinazoline derivatives with higher inhibitory activity, and in an analysis of their action mechanisms. It is noteworthy that this scheme would be very advantageous in factoring out precursors with excellent inhibitory activity via the computer ADDIT molecule-design, since all parameters in the QSAR equation are computable and controllable.
The optimized geometries, frequencies, and total electronic energies of two all-metal dianionic clusters Ga42- , In42- are calculated at the B3LYP, B3PW91, and MP2 levels of theory. There are two stable structures for each Ga42- , In42- species. For Ga42- , In42- species the square isomers are the most stable. On the basis of these computed stable structures we focus on two magnetic properties: magnetic susceptibility anisotropy and nucleus-independent chemical shift (NICS) for the square planar Ga42- , In42- isomers, which are calculated with B3LYP and HF methods. The computed results of NICS show that the square planar Ga42- , In42- isomers possess strong aromaticity. The detailed molecular orbital analysis for the two isomers further reveals that the two square planar Ga42- , In42- isomers have multiple-fold aromaticity: one delocalized π MOs and two delocalized σ MOs, which play important role in explaining the special stability of these all-metal square clusters.
The structure and growth trend of the protonated acetophenone-water clusters have been investigated using the DFT-B3LYP method combined with the standard 6-31+G(d,p) basis set. In order to obtain more accurate single-point energy the B3LYP/6-311++G(3df,2p) method was adapted. The results show that the formation of H+C8H8O-H2O is a barrierless reaction process and the equilibrium distance between the proton and the O atom in C8H8O molecule is 1.015 A. For H+C8H8O-(H2O)n(n=1,2,3) clusters, the proton lies between the acetophenone molecule C8H8O and the water molecule H2O. The distance between the proton and the O atom of the C8H8O molecule increased from n=1 to n=3; C8H8O-H+-H2O can be regarded as an solvation shell. For H+C8H8O(H2O)n (n=4,5,6,7,8) clusters, the proton lies between the two H2O molecules forming a H5O2+ structure, C8H8O-H5O2+ is an important structure, which the other H2O molecules will attack from different sides.
The influence of an external field on the ground states energy and dipole moment of the cyclic water trimer is investigated. Employing the Hartree-Fork method with basis sets 3-21G. The field-induced H-F force including the internal and external forces and clusters equilibrium structures under balance of this force are analyzed. The external field is varied in the 0.001~0.01 a.u. range. It is shown that the magnitude of the external electric field has important effects on these characteristics of the cyclic water trimer. The energy was found to decrease and the dipole moment to increase with the increasing external field. The change of the electronic population of every atom leads the electrostatic field to vary accordingly.
The hydrogen bond structure and interaction energy on the ground state of pyridazine and water complex are studied with B3LYP and MP2 method. All calculations show that there are strong interactions for a hydrogen bond N…H-O and large red-shifts for the symmetric H-O stretching vibrational frequencies in the pyridazine and water complex. The first singlet 1(n, π ) and 1(π,π) vertical excitations of the monomer pyridazine and the hydrogen bond between a pyridazine molecule and a water molecule have been investigated with time-dependent density functional theory TDB3LYP method.
The equilibrium geometries of the polyacrylonitrile (PAN) chain was theoretically studied using the Hartree-Fock method at the STO-3G levels. As for the optimized structures, the average distance of the C atom couple in the main chain is 155.6 pm; the average distance of the C atom couple in the branch chain is 149.7 pm; the average distance between a C atom bonding with N atom is 115.5 pm. For the charge distribution, because of the influence of a N atom with its comparatively larger negative charge, the C atoms in the main chain are different in their charge distribution. Finally, the vibration models of the chain have been analyzed to clarify the reaction sequence of dehydrogenation and cyclization during preoxidation and carbonization of the polyacrylonitrile.
Based on the Maxwell-Wagner model, an analytical formula for effective dielectric constants is derived as a series expansion in powers of the volume fraction of spheres. Effective dielectric constants of simple cubic lattices of conducting particles suspended in dielectric or conducting fluids are calculated. The numerical results show that effective dielectric constants depend upon the ratios of the permeability of conducting spheres to that of the suspending fluids under high frequency (0.1-1 kHz) applied fields, whereas, it is determined by the ratios of the conductivities of spheres to that of fluids under low frequency or dc electric fields. The imaginary parts of effective dielectric constants can be very big sometimes. This means that the resistive losses of electrorheological fluids can be very strong at times. The effect of conduction in a system cannot be neglected in the design of high performance electrorheological fluids.
On the basis of distributed chains, the model of MR elastomer was revised. After the potential energy of a chain was analyzed using the local field method, a special function was used to describe the distribution of chains. Then the MR effect of distributed chains as well as the overall MR effect were studied. Concurrently, the effects of the curing magnetic field and the matrix were incorporated into the model of MR elastomer.
The coupled dynamical model consisting of the electrode B-Z system, and its related bulk phase B-Z system externally controlled by a periodical current is proposed on the basis of the Oregonator model. Dynamical behaviors of the electrode B-Z system, when subjected to external current constraint have been investigated systematically under the condition that the bulk phase is at a steady state. Furthermore, by means of the analytic method of slow manifold the regimes favorable to the appearance of limit-cycle oscillation have been determined on both the current~concentration of BrO3- and the current~model parameter plane respectively. The results are similar to those of experiments controlled externally by weak-periodical potential constraint, as reported in former works. It turns out that a limited cycle oscillatory regime degenerates under external periodical current constraint. Meanwhile, a kind of forced oscillations emerges in the regime where limit-cycle oscillations can t appear under constant current constraint.
A simplified method, Laplace transformation, is used to discuss the radial Schrodinger equation with the weakest bound electron potential model (WBEPM). Through using such method, the second-order differential equation is reduced to a first-order differential equation and the exact bound state solutions including energy spectrum and normalized wave functions are obtained by making use of the integral. The results agree with those obtained by Zheng. It is most important that the two kinds of new recursion relations of radial wave functions are derived by the same method. These new recursion relations are the relations between the effective principal and angular-momentum quantum numbers, and are comprehensive in application to the calculations of transition probabilities in atomic and molecular physics.
A series of simulations of the crystallization and vitrification processes for metal Cu were carried out by means of the molecular dynamics technique. The radial distribution function, common neighbors, internal energy and volume of the system were recorded during the processes. The atomic internal energy, atomic Voronoi volume and atomic stress field of the relax system were analyzed at zero temperature. The interaction between atoms in the system is described using the embedded atom potential as proposed by Mishin. The simulation results show that crystalline and non-crystalline phases form at lower and higher cooling rates respectively. In comparison to nanocrystals, it is found that metallic glass has higher internal energy and larger volume. The intrinsic stress field is induced by distortion of the lattice.
The depletion force on a large hard sphere in a solvent of small hard spheres under geometrical confinement is investigated by using local density integration method through Monte Carlo simulations. The model considered here is a rectangular box with two boundless hard plates placed in a direction. Small hard spheres are randomly distributed in the box to form a hard sphere fluid. The number of small spheres is determined by the given volume fraction. The size ratio of the large to small-sphere is 5. Three systems maintained at bulk volume fractions 0.116, 0.229, and 0.341 are studied. The effects of geometrical confinement are taken into account through changing the distance of the two plates. To get rid of the finite size effect, the sizes of the box in other two directions are enlarged in a way when the distance between the two plates is decreased. The configurations of the small spheres are sampled according to the Metropolis algorithm with the two large spheres fixed at a separation. Each small sphere is chosen and relocated using a trial displacement. The new position is accepted so long as it does not result in an overlap with the large hard spheres, the other small spheres or the plates. To take the geometrical confinements into account, the fixed boundary condition is used corresponding to the two plates. Meanwhile the magnitude of the maximum random displacement is adjusted so that the overall acceptance ratio is about 0.3-0.5. The numerical results show that the depletion force is affected by the geometrical confinements. Furthermore, the nearer the two plates are to each other, the larger the effects from the geometrical confinement will be.
A class of excitable media described by the Fitzhugh-Nagumo equation is investigated. Based on the stable and selfadaptive theory, the error between the systems grid variables and the standard sampling of the periodical signal or constant signal was feed back into the system both globally and locally. When the controller was then shut off, automatically, the whole system became homogeneous. Additionally, the scheme was tested under noisy conditions. The numerical simulations results demonstrate its effectiveness. The system reached a homogeneous state and a spiral wave was converted into a target wave, resulting in a wonderful pattern emerging using a different controller. The scheme proved robust in resisting the effects of noise.
Stretching and relaxation of a single DNA molecule tethered in a specially designed thin slit were studied using Monte Carlo simulation combined with bondfluctuation method. It was found that the extension and relaxation of the single DNA molecule are greatly affected by the confined environment. If the extent of the confined environment is increased by decreasing the distance between the two planar surfaces of the slit, the extension of the single DNA molecule increases, due to the screening of the hydrodynamic interaction of DNA segments by the planar surfaces of the slit. The relaxation of the single DNA molecule in different confined environments verifies this assumption completely. The correlation between the end-to-end separation and flow velocity obtained by Monte Carlo simulation is in good agreement with either the experimental results or theoretical consideration reported previously.
Rare earth composite cobalt ferrite ionic magnetic fluids were prepared by precipitation in the presence of Tri-sodium citrate. The sample phase, structure and particle sizes were determined by X-ray diffraction transmission and electron microscopy. It is clear that the particles appear as variously sized balls, Cobalt ferrite with sizes of 12-15 nm, Dysprosium cobalt ferrite and Yttrium cobalt ferrite with sizes of 6-8 nm. By adding rare earth ions, the average diameter of the magnetic nanoparticles was decreased. The decrease in diameter was explained using a micro-model of rare earth modification. The effect of rare earth ion modification on the saturation magnetization and magnetic induction of magnetic fluids was carried out using a Gouy magnetic balance and a spectrophotometer. The result shows that saturation magnetization and magnetic induction can be improved by adding Dy3+. By adding Y3+, magnetic induction was increased. However, the saturation magnetization then decreased. A theory of the mechanism of rare earth ion modification is discussed in detail.
SnO2 nanocrystal with different crystalline sizes were prepared with SnCl2 2H2O and H2O2 raw materials by a hydrothermal process. The synthesized powders at different reaction temperatures were characterized by means of powder X-ray diffraction, transmission electron microscope, specific surface area and gas sensitivity measurements. The results revealed that the pure SnO2 nanocrystallites synthesized at 120 ℃ have high specific surface area (210.3 m2/g), and show a high sensitivity to C2H5OH gas. Both traits are beneficial in gas-sensitive detection application.
Different size platinum nanoparticles, ranging in size from 1.8-14.1 nm, were prepared by multi-step reduction of H2PtCl6 by hydrogen adsorbed on platinum atoms. Transmission electronic microscopy and X-ray diffraction were used to characterize the nanoparticles. After thirty-two iterations of the reaction, the diameter of platinum nanoparticles increased from 1.8 nm to 14.1 nm. The average iterative increase was approximately 0.4 nm. The size distribution of the nanoparticles was narrow. Synthesis procedures which allow for control of platinum nanoparticle size offer the possibility for the further research into how the sizes of nano-catalysts effect catalytic activity.
The nano-phase microstructure of high molecular weight poly(ε-caprolactone) (PCL) /silica hybrid materials, in which polymeric and inorganic component are coupled by hydrogen bonding, and nucleation and growth of PCL chain in the hybrids were studied by scanning electronic microscopy, wide-angle X-ray diffraction and differential scanning calorimetry. The results show that the micro-phase separation in the hybrids occurs at the nano-meter scale. The average scale of the polymeric domain is about 70 nm. The morphological structure of the inorganic component appears as irregular particles. The uniform distribution of two phases relates to the bonding strength of hydrogen bonding between components in the hybrids. After a PCL is hybridized, the relative degree of crystallinity decreases and the corresponding scale of microlite change. In addition, with inorganic content increasing, the equilibrium melting points of the PCL in hybrids decrease. The energy that polymeric chains fold to form crystals on the surface of crystal nucleus increases. This result is due to the influence of silica and the bonding strength in hybrids.
Silver iodide nanoclusters were successfully prepared in the channels of NaZSM-5 zeolite by a thermal diffusion method. Chemical analysis, powder X-ray diffraction, nitrogen adsorption technique, and infrared spectroscopy were used to characterize the prepared samples. The solid diffuse reflectance absorption spectra and luminescence properties were studied. Chemical analysis showed that the guest silver iodide was incorporated into the host NaZSM-5. Powder X-ray diffraction analysis showed that the framework of NaZSM-5 still remained in the (NaZSM-5)-AgI samples. Infrared spectra indicate that the vibration of the framework of NaZSM-5 had little variation attributable to the encapsulation of AgI in the host. This phenomenon is due to the incorporation of silver iodide into NaZSM-5. Investigation of the absorption revealed that the guest silver iodide was encapsulated in the channels of NaZSM-5. Solid diffuse reflectance absorption spectra indicated that the absorption of prepared (NaZSM--5)-AgI host-gust samples had nothing with the host NaZSM-5. The absorption spectra of the (NaZSM-5)-AgI samples were influenced by the size of AgI nanoclusters. Luminescence investigation showed that the prepared samples had a high energy band gap and a strong radiation process. The (NaZSM-5)-AgI samples are luminescient composite materials.
ZnO films were deposited on glass substrates by gas discharge reaction evaporation. The influences of substrate temperature on the surface morphology, crystal structure and electric properties of ZnO films were studied by scanning electron microscopy, atomic force microscopy, X-ray diffraction spectroscopy and complex impedance spectroscopy. The results show that the films with dense and amorphous structure and lower grain boundary resistance were deposited at room temperature. When the substrate temperature is higher than 50 ℃, the films with certain c-axis orientation can be deposited. With the increase of the substrate temperature, the preferential orientation of ZnO films along c-axis is augmented, the tensile stress along c-axis orientation decreases and the grain boundary resistance increases in a marked degree. When the substrate temperature is higher than 100 ℃, the increasing trend of the preferential orientation of ZnO films along c-axis slows down. ZnO films possess high preferential c-axis orientation and best crystalline quality at 180-200 ℃. These possess a smooth surface, symmetrical grain dimension (i.e. 30-40 nm), inerratic crystal shape, less tensile stress and 0.965 epitaxial degree along the c-axis direction. Here the grain boundary effect increases and the grain boundary resistance is evidently more than that of the films deposited at room temperature. The mechanism by which substrate temperature affects crystal structure and grain boundary properties were also discussed.
Water soluble multi-wall carbon nanotubes (MWCNTs) were prepared via chemical oxidation. Under ultrasonication,the chemically treated MWCNTs can be dispersed in water to form colloids. The MWCNTs were characterized by FT-IR spectra. The FT-IR spectra reveal the presence of carboxylic groups on the nanotubes. The functional groups can improve the nanotubes-solubility in water. Alcian Blue 8GX (AB), a quaternary ammonium dye of the copper phthalocyanine group, was dissolved in water and used to form electrostaticcally self-assembled multilayer films. The MWCNT/AB composite films were characterized by UV-vis absorption spectra as well as AFM and fluorescence spectrum. The experimental results show that the MWCNT/AB composite films can be produced easily. Compared to those of the AB aqueous solutions, composite films exhibit pronounced differences in the absorption and fluorescence spectra, which suggests that AB molecules aggregated in the composite film, and that a chargetransfer might exist between AB molecules and the MWCNTs.
Amorphous and oriented polycrystalline LiCoO2 thin films, used as cathode material for an all-solid-state thin film battery, were fabricated by using RF magnetron sputtering and annealed at different temperatures. The morphology and structure of LiCoO2 thin films were characterized by scanning electron microscopy and X-ray diffraction. All-solid-state thin film batteries, comprised of LiCoO2 cathode films with different structures, lithium phosphorous oxynitride electrolyte film and metallic lithium anode film, was successfully prepared and their properties were examined by chronopotentiometry. Results showed that the structure and crystallinity of the LiCoO2 films strongly influenced the electrochemical performance of all-solid-state thin film lithium batteries. Worth nothing was the battery with an oriented polycrystalline LiCoO2 film it exhibited the best electrochemical performance, and delivered a discharge capacity of ~55.4 μAh/cm2μm. Furthermore, when subjected to over 450 charge/discharge cycles, that battery suffered no obvious fode in capacity.
The adsorption and dissociation of hydrogen on stepped surface (511) of nickel are studied with the embedded-atom model (EAM) method. The adsorption energy, the length of the adsorption bond and the adsorption height for a single hydrogen atom are calculated. Three kinds of stable sites are found for hydrogen adsorption. There are the double-fold bridge site B on the step edge, the three-fold hollow site H3′ on the step surface and the four-fold hollow sites H1 and H2 on the terrace surface. Compared with a hydrogen atom adsorbed on low-index (001) surface, there are two other adsorption sites near the step: the two-fold bridge site B on the step edge and the three-fold hollow site H3′ on the step surface. At the same time, the absorbability of the hydrogen atom at the site H1 is intensified. The results show that hydrogen adsorption on Ni (511) is affected by the existence of the step. The active barriers, adsorption energy and corresponding bond length for dissociation of a hydrogen molecule on the stepped surface are presented. The results show that the dissociation is easier at the bottom of the step. It is shown that the steps are the active sites for hydrogen adsorption and dissociation.
Nanocrystalline zinc phosphate tetrahydrate was synthesized by solid-state reaction at ambient temperature using Na3PO4·12H2O and ZnSO4·7H2O as regents. The enthalpy of reaction and the standard enthalpy of formation of zinc phosphate tetrahydrate were studied by microcalorimeter. According to Hess s law, a new thermochemical cycle was designed. The dissolution enthalpies of reactant (△H1) and product (△H2) were performed by a RD496 microcalorimeter at 298.15 K using aqueous solution of hydrochloric acid (4mol/L) as a calorimetric solvent. Ultraviolet spectrum, conductivity and refractive index were measured respectively. The results show as follows: △H1=(-47.180±0.084) kJ/mol, △H2=(-7.617±0.096 )kJ/mol. The ultraviolet spectra of the above solution are the same. Conductivity values after 500 times diluted are 2180 and 2181μs/cm respectively. Refractive indexes are 1.3679 and 1.3678 respectively. The standard enthalpy value of the reaction was calculated: △rHm=-39.530 kJ/mol. The standard enthalpy of formation for zinc phosphate tetrahydrate are recommended -4354.004 kJ/mol.
Cerium incorporated MCM-48 molecular sieves have been hydrothermally synthesized by both a mixed template and a variable pH approach. The samples were characterized by various physicochemical methods, including X-ray diffraction, transmission electron microscopy, diffuse reflectance UV-vis spectroscopy, XRF spectroscopy, nitrogen adsorption. These results reveal that cerium is incorporated in MCM-48 in the form of well-dispersed tetra-coodinated cerium ion. Maintaining the proper concentration of cerium and adjusting the pH allows for a more ordered structure with a much higher specific surface area than that of MCM-48. Ce-MCM-48 was employed in the liquid phase oxidation of cyclohexane with aqueous H2O2. The results showed that Ce-MCM-48 is more active as a catalyst for the liquid phase oxidation of cyclohexane. The oxidation conversion catalyzed by Ce-MCM-48 is 8.3 %-14.2% higher than that catalyzed by MCM-48 and the selectivity for the main products increase by 63.4%-68.8%. Accordingly, Ce-MCM-48 has been shown to have important potential applications.