Quantum dynamics study of isotope effect for H+CH4 reaction using the SVRT model

The semirigid vibrating rotor target model is applied to study the isotope effect in reaction H + CH4-->H-2 + CH3 using time-dependent wave-packet method. The reaction probabilities for producing H-2 and HD product channels are calculated. The energy dependence of the reaction probabilities shows oscillating structures for both reaction channels. At low temperature or collision energies, the H atom abstraction is favored due to tunnelling effect. In partially deuterated CHxDy (x + y = 4), the breaking of the C-H bond is favored over that of the C-D bond in the entire energy range studied. In H + CHD3 reaction at high energies, the HD product dominates simply due to statistical factor. (C) 2003 American Institute of Physics.

Theoretical study on the ClO/ClO- system electron-transfer reactivity by the golden-rule

The structures, properties and electron transfer reactivity of the ClO/ClO- coupling system are studied in this paper at ab initio (UHF and UMP2) levels and the Density Functional Theory (DFT: UB3LYP, UB3P86, UB3PW91) levels employing 6311 + G(3df) basis set and on the basis of the Golden-rule of the time-dependent perturbation theory. Investigations indicate that the results obtained using the UB3LYP method employing 6-311 + G(3df) basis set is in excellent agreement with the experiment. For this coupling system, six stable coupling modes have been found which correspond to six different encounter complexes and denote six different electron transfer mechanism: four O-O directly linked structures (one collinear: D-h, one anti-parallel: C-s, two twist: C-2) and two Cl-O linked structures (cis- and anti- C-s structures). The activation energies, the stabilization energies and the electronic coupling matrix elements have also been calculated for the electron transfer reactions via these six different mechanism at the UB3LYP/6-311 + G(3df) level, and then the electron transfer rates are determined at the same level. The most favorable coupling mode to the electron transfer is the anti-parallel mechanism. The averaged electron transfer rate is about 5.58 X 10(11) M-1 s(-1). It is also implied that the B3LYP method can give more reasonable results for the electron transfer reactivity of this system. (C) 2003 Elsevier B.V. All rights reserved.

Collisional quantum interference effect on rotational energy transfer in an atom-diatom system

The theoretical model of collisional quantum interference (CQI) in intramolecular rotational energy transfer is described in an atom-diatom system, based on the first Born approximation of time-dependent perturbation theory and considering a long-range interaction potential. The relation between differential and integral interference angles is obtained. For the CO A(1)Pi (v = 0)/e(3)Sigma (-)(v = 1)-He collision system, the calculated integral interference angles are consistent with the experimental values. The physical significance of interference angle and the essential factors it depends on as well as the influence of the short-range interaction on CQI are discussed. (C) 2001 Elsevier Science B.V. All rights reserved.

Effects of the transition dipole moment function on the dynamics of ozone photodissociation: an exact 3D quantum mechanical study

The effects of the transition dipole moment function (TDMF) on the dynamics Of O-3 photodissociation in the Hartley band have been exploited by means of exact 3D time-dependent wavepacket method using the SW potential energy surface [J. Chem. Phys. 78 (1983) 7191]. The calculations show that the explicit inclusion of the TDMF results in slight uniform reductions for the intensities of recurrence peaks of the autocorrelation function and a slight broadening of the absorption spectrum, in comparison with the result where the TDMF is assumed to be constant. The pattern of recurrence structures of the autocorrelation function is essentially unaffected. (C) 2001 Elsevier Science B.V. All rights reserved.

Multipolar model for collisional quantum interference on rotational energy transfer

A theoretical model of collisional quantum interference (CQI) is developed in a diatom-diatom system based on the first-order Born approximation of time-dependent perturbation theory and the multipolar interaction potential. The transition cross section is obtained. The relations between the differential and integral interference angles are discussed. The key factors on the determination of the differential and integral interference angles are obtained. The changing tendency of the interference angles with the experimental temperatures is obtained.

水流作用下疏松土壤材料中细沟的再生及其临界剪应力的实验研究

动态土壤侵蚀包括依赖于空间与时间的土壤剥离、细沟的形成、水流中过量泥沙的沉积、沉积泥沙中细沟的再生等物理过程。与泥沙从沉积区域再剥离相关联的细沟再生是细沟变窄加深过程中的一个重要的现象。该文介绍一种实验装置 ,用于测量类似于沉积土壤的疏松土壤材料细沟再生的力学参数。用一种沙壤土进行实验 ,测定了不同团聚体大小和坡度下细沟再生开始和停止所对应的临界水流量。计算出了与沟坡相关的临界剪切应力。这些结果有助于理解细沟的再生及其数量关系 ,以及临界剪切应力与坡度间的定量关系 ;对于发展由沉积土壤再生的细沟演化过程模型特别有用。

GIUSAXS and AFM Studies on Surface Reconstruction of Latex Thin Films during Thermal Treatment

The structural evolution of a single-layer latex film during annealing was studied via grazing incidence ultrasmall-angle X-ray scattering (GIUSAXS) and atomic force microscopy (AFM). The latex particles were composed of a low-T-g (-54 degrees C) core (n-butylacrylate, 30 wt %) and a high-T-g (41 degrees C) shell (t-butylacrylate, 70 wt %) and had an overall diameter of about 500 nm. GIUSAXS data indicate that the q(y) scan at q(z) = 0.27 nm(-1) (out-of-plane scan) contains information about both the structure factor and the form factor. The GIUSAXS data on latex films annealed at various temperatures ranging from room temperature to 140 degrees C indicate that the structure of the latex thin film beneath the surface changed significantly. The evolution of the out-of-plane scan plot reveals the surface reconstruction of the film. Furthermore, we also followed the time-dependent behavior of structural evolution when the latex film was annealed at a relatively low temperature (60 degrees C) where restructuring within the film can be followed that cannot be detected by AFM, which detects only surface morphology.

The adsorption of dopamine on gold and its interactions with iron(III) ions studied by microcantilevers

The adsorption of dopamine (DA) molecules on gold and their interactions with Fe3+ were studied by a microcantilever in a flow cell. The microcantilever bent toward the Au side with the adsorption of DA due to the change Of Surface stress induced by the intermolecular hydrogen bonds of DA or the charge transfer effect between adsorbates and the Substrate. The interaction process between DA adsorbates and Fe3+ was revealed by the deflection curves of microcantilever. As indicated by the appearance of a variation during the decline of curves, two steps were observed in the curve at relative high concentrations of Fe3+. In this case, Fe3+ reacted with DA molecules only in the outer layers and the complexes removed with solution. Then Fe3+ reacted further with DA molecules forming the surface complex in the first layer next to the gold. At this stage, the stability Of Surface complexes was time dependent, i.e., unstable initially and stable finally. This may be due to the surface complexes change from mono-dentate to bi-dentate complexes. In another case, i.e., at relative low concentration of Fe3+, only the first step was observed as indicated by the absence of a variation.

Facile Hydrothermal Synthesis and Luminescent Properties of Large-Scale GdVO4:Eu3+ Nanowires

Large-scale GdVO4:Eu3+ nanowires with diameters of about 15 nm and lengths of several micrometers were achieved by a facile hydrothermal method in the presence of disodium ethylenediamine tetraacetate (Na2H2L). The influences of several parameters, such as pH value, reaction temperature, and molar ratio of Na2H2L to Gd3+ on the final products were investigated. The formation mechanism of the as-obtained GdVO4:Eu3+ nanowires is proposed on the basis of time-dependent experiments. It is found that the organic additive Na2H2L, which acts as a shape modifier, has a dynamic effect by adjusting the growth rates of different facets, resulting in the formation of the GdVO4:Eu3+ nanowires. The luminescent spectrum of GdVO4:Eu3+ nanowires shows the strong characteristic dominant emission of the Eu3+ ions at 614 nm.

Facile shape-controlled synthesis of luminescent europium benzene-1,3,5-tricarboxylate architectures at room temperature

The large-scale synthesis of the metal-organic framework Eu(1,3,5-BTC)center dot 6H(2)O nanocrystallites with delicate morphologies such as sheaflike, butterflylike, and flowerlike superstructures composed of nanowires have been realized via a simple solution phase method at room temperature. Time-dependent experiments indicate that these superstructures were constructed by the splitting crystal growth mechanism, as has been noted in some minerals in nature. The synthetic parameters such as reaction time, concentration and molar ratio of reactants, surfactant, and reaction temperature all affected the morphology of the Eu(1,3,5-BTC)center dot 6H(2)O architectures. These well-arranged architectures exhibit red emission corresponding to the D-5(0) -> F-7(2) transition of the Eu3+ ions under UV light excitation, and the lifetime is determined to be about 0.22 ms.

Study on the Single Crystals of Poly(3-octylthiophene) Induced by Solvent-Vapor Annealing

Needle-like single crystals of poly(3-octylthiophene) (P3OT) have been prepared by tetrahydrofuran-vapor annealing. The morphology and structure of the crystals were characterized with optical microscopy, scanning electron microscopy, atomic force microscopy, transmission electron microscopy, and wide-angle X-ray diffraction. It is observed that the P3OT molecules are packed with the backbones parallel to the length axis of the crystal and the alkyl side chains perpendicular to the substrate. The field effect transistor based on the P3OT single crystal exhibited a charge carrier mobility of 1.54 x 10(-4) cm(2)/(Vs) and on/off current ratio of 37, and the molecular orientation of the crystal is ascribed to account for the device performance. The time-dependent morphological evolution demonstrated that the crystals underwent Ostwald ripening when annealed.

Single molecule dynamics and statistical fluctuations of gene regulatory networks: A repressilator

The authors developed a time dependent method to study the single molecule dynamics of a simple gene regulatory network: a repressilator with three genes mutually repressing each other. They quantitatively characterize the time evolution dynamics of the repressilator. Furthermore, they study purely dynamical issues such as statistical fluctuations and noise evolution. They illustrated some important features of the biological network such as monostability, spirals, and limit cycle oscillation. Explicit time dependent Fano factors which describe noise evolution and show statistical fluctuations out of equilibrium can be significant and far from the Poisson distribution. They explore the phase space and the interrelationships among fluctuations, order, amplitude, and period of oscillations of the repressilators. The authors found that repressilators follow ordered limit cycle orbits and are more likely to appear in the lower fluctuating regions. The amplitude of the repressilators increases as the suppressing of the genes decreases and production of proteins increases. The oscillation period of the repressilators decreases as the suppressing of the genes decreases and production of proteins increases.

Effects of casting solvents on the formation of inverted phase in block copolymer thin films

Previously, an inverted phase (the minority blocks comprising the continuum phase) was found in solution-cast block copolymer thin films. In this study, the effect of casting solvents on the formation of inverted phase has been studied. Two block copolymers, poly(styrene-b-butadiene) (SB) (M-w = 73 930 Da) and poly(styrene-b-butadiene-b-styrene) (SBS) (M-w = 140 000 Da), with comparable block lengths and equal polystyrene (PS) weight fraction (similar to30 wt %) were used. The copolymer thin films were cast from different solvents, toluene, benzene, cyclohexane, and binary mixtures of benzene and cyclohexane. Toluene and benzene are good solvents for both PS and PB, but have a preferential affinity for PS, while cyclohexane is a good solvent for PB but a Theta solvent for PS (T-Theta = 34.5 degreesC). The differential solvent affinity for PS and PB was estimated in terms of a difference between the polymer-solvent interaction parameter, chi, for each block. Under an extremely slow solvent evaporation rate, the time-dependent phase behavior during such a solution-to-film process was examined by freeze-drying the samples at different stages, corresponding to different copolymer concentrations, rho.

Effect of annealing on the viscoelastic and viscoplastic responses of low-density polyethylene

Two series of tensile tests with constant crosshead speeds (ranging from 5 to 200 mm/min) and tensile relaxation tests (at strains from 0.03 to 0.09) were performed on low-density polyethylene in the subyield region of deformations at room temperature. Mechanical tests were carried out on nonannealed specimens and on samples annealed for 24 h at the temperatures T = 50, 60, 70, 80, and 100 degreesC. Constitutive equations were derived for the time-dependent response of semicrystalline polymers at isothermal deformations with small strains. A polymer is treated as an equivalent heterogeneous network of chains bridged by temporary junctions (entanglements, physical crosslinks, and lamellar blocks). The network is thought of as an ensemble of mesoregions linked with each other. The viscoelastic behavior of a polymer is modeled as a thermally induced rearrangement of strands (separation of active strands from temporary junctions and merging of dangling strands with the network). The viscoplastic response reflects sliding of junctions in the network with respect to their reference positions driven by macrostrains. Stress-strain relations involve five material constants that were found by fitting the observations.

The viscoelastic and viscoplastic behavior of low-density polyethylene

Three series of tensile tests with constant cross-head speeds (ranging from 5 to 200 mm/min), tensile relaxation tests (at strains from 0.03 to 0.09) and tensile creep tests (at stresses from 2.0 to 6.0 MPa) are performed on low-density polyethylene at room temperature. Constitutive equations are derived for the time-dependent response of semicrystalline polymers at isothermal deformation with small strains. A polymer is treated as an equivalent heterogeneous network of chains bridged by temporary junctions (entanglements, physical cross-links and lamellar blocks). The network is thought of as an ensemble of meso-regions linked with each other. The viscoelastic behavior of a polymer is modelled as thermally-induced rearrangement of strands (separation of active strands from temporary junctions and merging of dangling strands with the network). The viscoplastic response reflects mutual displacement of meso-domains driven by macro-strains. Stress-strain relations for uniaxial deformation are developed by using the laws of thermodynamics. The governing equations involve five material constants that are found by fitting the observations. Fair agreement is demonstrated between the experimental data and the results of numerical simulation.