Information Preservation (IP) Method in Simulation

This paper reviews firstly methods for treating low speed rarefied gas flows: the linearised Boltzmann equation, the Lattice Boltzmann method (LBM), the Navier-Stokes equation plus slip boundary conditions and the DSMC method, and discusses the difficulties in simulating low speed transitional MEMS flows, especially the internal flows. In particular, the present version of the LBM is shown unfeasible for simulation of MEMS flow in transitional regime. The information preservation (IP) method overcomes the difficulty of the statistical simulation caused by the small information to noise ratio for low speed flows by preserving the average information of the enormous number of molecules a simulated molecule represents. A kind of validation of the method is given in this paper. The specificities of the internal flows in MEMS, i.e. the low speed and the large length to width ratio, result in the problem of elliptic nature of the necessity to regulate the inlet and outlet boundary conditions that influence each other. Through the example of the IP calculation of the microchannel (thousands long) flow it is shown that the adoption of the conservative scheme of the mass conservation equation and the super relaxation method resolves this problem successfully. With employment of the same measures the IP method solves the thin film air bearing problem in transitional regime for authentic hard disc write/read head length ( ) and provides pressure distribution in full agreement with the generalized Reynolds equation, while before this the DSMC check of the validity of the Reynolds equation was done only for short ( ) drive head. The author suggests degenerate the Reynolds equation to solve the microchannel flow problem in transitional regime, thus provides a means with merit of strict kinetic theory for testing various methods intending to treat the internal MEMS flows.

Information preservation (IP) method in simulation of internal rarefied gas flows in MEMS

This paper reviews firstly methods for treating low speed rarefied gas flows: the linearised Boltzmann equation, the Lattice Boltzmann method (LBM), the Navier-Stokes equation plus slip boundary conditions and the DSMC method, and discusses the difficulties in simulating low speed transitional MEMS flows, especially the internal flows. In particular, the present version of the LBM is shown unfeasible for simulation of MEMS flow in transitional regime. The information preservation (IP) method overcomes the difficulty of the statistical simulation caused by the small information to noise ratio for low speed flows by preserving the average information of the enormous number of molecules a simulated molecule represents. A kind of validation of the method is given in this paper. The specificities of the internal flows in MEMS, i.e. the low speed and the large length to width ratio, result in the problem of elliptic nature of the necessity to regulate the inlet and outlet boundary conditions that influence each other. Through the example of the IP calculation of the microchannel (thousands m ? long) flow it is shown that the adoption of the conservative scheme of the mass conservation equation and the super relaxation method resolves this problem successfully. With employment of the same measures the IP method solves the thin film air bearing problem in transitional regime for authentic hard disc write/read head length ( 1000 L m ? = ) and provides pressure distribution in full agreement with the generalized Reynolds equation, while before this the DSMC check of the validity of the Reynolds equation was done only for short ( 5 L m ? = ) drive head. The author suggests degenerate the Reynolds equation to solve the microchannel flow problem in transitional regime, thus provides a means with merit of strict kinetic theory for testing various methods intending to treat the internal MEMS flows.

Kinetic Study Of The Rayleigh-Benard Flows

The present paper employs the direct simulation Monte Carlo (DSMC) method to study the Rayleigh-Benard flows, where the temperature ratio of the upper to lower plate is fixed to 0.1. For a Knudsen number (Kn) of 0.01, as the Rayleigh number (Ra) increases, the flow changes from the thermal conductive state to the convective state at about Ra=1700, and the calculated relation of heat flux through the lower plate versus Ra is in good agreement with classical experimental and theoretical results. For Kn=0.05, the thermal conductive state remains stable, and the increase of Ra cannot trigger thermal instability.

Kinetic studies of gas flows

Our recent studies on kinetic behaviors of gas flows are reviewed in this paper. These flows have a wide range of background, but share a common feature that the flow Knudsen number is larger than 0.01. Thus kinetic approaches such as the direct simulation Monte Carlo method are required for their description. In the past few years, we studied several micro/nano-scale flows by developing novel particle simulation approach, and investigated the flows in low-pressure chambers and at high altitude. In addition, the microscopic behaviors of a couple of classical flow problems were analyzed, which shows the potential for kinetic approaches to reveal the microscopic mechanism of gas flows.

Kinetic theory of normal quantum fluids

Close to equilibrium, a normal Bose or Fermi fluid can be described by an exact kinetic equation whose kernel is nonlocal in space and time. The general expression derived for the kernel is evaluated to second order in the interparticle potential. The result is a wavevector- and frequency-dependent generalization of the linear Uehling-Uhlenbeck kernel with the Born approximation cross section.

The theory is formulated in terms of second-quantized phase space operators whose equilibrium averages are the n-particle Wigner distribution functions. Convenient expressions for the commutators and anticommutators of the phase space operators are obtained. The two-particle equilibrium distribution function is analyzed in terms of momentum-dependent quantum generalizations of the classical pair distribution function h(k) and direct correlation function c(k). The kinetic equation is presented as the equation of motion of a two -particle correlation function, the phase space density-density anticommutator, and is derived by a formal closure of the quantum BBGKY hierarchy. An alternative derivation using a projection operator is also given. It is shown that the method used for approximating the kernel by a second order expansion preserves all the sum rules to the same order, and that the second-order kernel satisfies the appropriate positivity and symmetry conditions.

Part I. Influence of membrane morphology on ion-exchange and charge propagation in composite polyelectrolyte electrode coatings. Part II. Dynamic surface tension measurements of polarization relaxation at mercury pool electrodes by the method of Wilhelmy.

Part I. Novel composite polyelectrolyte materials were developed that exhibit desirable charge propagation and ion-retention properties. The morphology of electrode coatings cast from these materials was shown to be more important for its electrochemical behavior than its chemical composition.

Part II. The Wilhelmy plate technique for measuring dynamic surface tension was extended to electrified liquid-liquid interphases. The dynamical response of the aqueous NaF-mercury electrified interphase was examined by concomitant measurement of surface tension, current, and applied electrostatic potential. Observations of the surface tension response to linear sweep voltammetry and to step function perturbations in the applied electrostatic potential (e.g., chronotensiometry) provided strong evidence that relaxation processes proceed for time-periods that are at least an order of magnitude longer than the time periods necessary to establish diffusion equilibrium. The dynamical response of the surface tension is analyzed within the context of non-equilibrium thermodynamics and a kinetic model that requires three simultaneous first order processes.

Kinetic investigations of heterogeneously catalyzed reactions on the Ru(001) and Pt(110)-(1x2) surfaces

The initial probabilities of activated, dissociative chemisorption of methane and ethane on Pt(110)-(1 x 2) have been measured. The surface temperature was varied from 450 to 900 K with the reactant gas temperature constant at 300 K. Under these conditions, we probe the kinetics of dissociation via trapping-mediated (as opposed to 'direct') mechanism. It was found that the probabilities of dissociation of both methane and ethane were strong functions of the surface temperature with an apparent activation energies of 14.4 kcal/mol for methane and 2.8 kcal/mol for ethane, which implys that the methane and ethane molecules have fully accommodated to the surface temperature. Kinetic isotope effects were observed for both reactions, indicating that the C-H bond cleavage was involved in the rate-limiting step. A mechanistic model based on the trapping-mediated mechanism is used to explain the observed kinetic behavior. The activation energies for C-H bond dissociation of the thermally accommodated methane and ethane on the surface extracted from the model are 18.4 and 10.3 kcal/mol, respectively.

The studies of the catalytic decomposition of formic acid on the Ru(001) surface with thermal desorption mass spectrometry following the adsorption of DCOOH and HCOOH on the surface at 130 and 310 K are described. Formic acid (DCOOH) chemisorbs dissociatively on the surface via both the cleavage of its O-H bond to form a formate and a hydrogen adatom, and the cleavage of its C-O bond to form a carbon monoxide, a deuterium adatom and an hydroxyl (OH). The former is the predominant reaction. The rate of desorption of carbon dioxide is a direct measure of the kinetics of decomposition of the surface formate. It is characterized by a kinetic isotope effect, an increasingly narrow FWHM, and an upward shift in peak temperature with Ɵ_T, the coverage of the dissociatively adsorbed formic acid. The FWHM and the peak temperature change from 18 K and 326 K at Ɵ_T = 0.04 to 8 K and 395 K at Ɵ_T = 0.89. The increase in the apparent activation energy of the C-D bond cleavage is largely a result of self-poisoning by the formate, the presence of which on the surface alters the electronic properties of the surface such that the activation energy of the decomposition of formate is increased. The variation of the activation energy for carbon dioxide formation with Ɵ_T accounts for the observed sharp carbon dioxide peak. The coverage of surface formate can be adjusted over a relatively wide range so that the activation energy for C-D bond cleavage in the case of DCOOH can be adjusted to be below, approximately equal to, or well above the activation energy for the recombinative desorption of the deuterium adatoms. Accordingly, the desorption of deuterium was observed to be governed completely by the desorption kinetics of the deuterium adatoms at low Ɵ_T, jointly by the kinetics of deuterium desorption and C-D bond cleavage at intermediate Ɵ_T, and solely by the kinetics of C-D bond cleavage at high Ɵ_T. The overall branching ratio of the formate to carbon dioxide and carbon monoxide is approximately unity, regardless the initial coverage Ɵ_T, even though the activation energy for the production of carbon dioxide varies with Ɵ_T. The desorption of water, which implies C-O bond cleavage of the formate, appears at approximately the same temperature as that of carbon dioxide. These observations suggest that the cleavage of the C-D bond and that of the C-O bond of two surface formates are coupled, possibly via the formation of a short-lived surface complex that is the precursor to to the decomposition.

The measurement of steady-state rate is demonstrated here to be valuable in determining kinetics associated with short-lived, molecularly adsorbed precursor to further reactions on the surface, by determining the kinetic parameters of the molecular precursor of formaldehyde to its dissociation on the Pt(110)-(1 x 2) surface.

Overlayers of nitrogen adatoms on Ru(001) have been characterized both by thermal desorption mass spectrometry and low-energy electron diffraction, as well as chemically via the postadsorption and desorption of ammonia and carbon monoxide.

The nitrogen-adatom overlayer was prepared by decomposing ammonia thermally on the surface at a pressure of 2.8 x 10^(-6) Torr and a temperature of 480 K. The saturated overlayer prepared under these conditions has associated with it a (√247/10 x √247/10)R22.7° LEED pattern, has two peaks in its thermal desorption spectrum, and has a fractional surface coverage of 0.40. Annealing the overlayer to approximately 535 K results in a rather sharp (√3 x √3)R30° LEED pattern with an associated fractional surface coverage of one-third. Annealing the overlayer further to 620 K results in the disappearance of the low-temperature thermal desorption peak and the appearance of a rather fuzzy p(2x2) LEED pattern with an associated fractional surface coverage of approximately one-fourth. In the low coverage limit, the presence of the (√3 x √3)R30° N overlayer alters the surface in such a way that the binding energy of ammonia is increased by 20% relative to the clean surface, whereas that of carbon monoxide is reduced by 15%.

A general methodology for the indirect relative determination of the absolute fractional surface coverages has been developed and was utilized to determine the saturation fractional coverage of hydrogen on Ru(001). Formaldehyde was employed as a bridge to lead us from the known reference point of the saturation fractional coverage of carbon monoxide to unknown reference point of the fractional coverage of hydrogen on Ru(001), which is then used to determine accurately the saturation fractional coverage of hydrogen. We find that ƟSAT/H = 1.02 (±0.05), i.e., the surface stoichiometry is Ru : H = 1 : 1. The relative nature of the method, which cancels systematic errors, together with the utilization of a glass envelope around the mass spectrometer, which reduces spurious contributions in the thermal desorption spectra, results in high accuracy in the determination of absolute fractional coverages.

Kinetic spectra of light-adaptation dark-adaptation and M-intermediate of BR-D96N

BR-D96N is a kind of genetically site-specific mutants of bacteriorhodopsin (BR) with obvious photochromic effect. Compared to the wild type BR, the lifetime of M state of BR-D96N is prolonged to several minutes so that the photochromic kinetics and the intermediates formation can be studied by the conventional spectra analysis. In the experiment, the absorption spectra of the sample at different time after light illumination are measured with spectrophotometer. By fitting and analyzing the variation of the spectra, we suppose that there are three main states in the, photochromic process, i.e., B state (light-adapted state), M state and D state (dark-adapted state). The absorption spectra of the B state, M state and D state are extracted from the experimental data based on this three-state model and the spectra at various time are fitted with the least-square method. So, the variations of population percentages of the M state, B state and D state are obtained and the M state and B state lifetimes are estimated. In another way, from the measurement of the absorption dynamics at 407 and 568 nm, the M state and B state lifetimes are also obtained by two exponential data fitting, which give coincident results with those of the spectra analysis. (C) 2003 Elsevier Science B.V. All rights reserved.

Photochromic kinetic spectra and intermediates of BR-D96N

BR-D96N is a kind of genetically site-specific mutant of bacteriorhodopsin (BR) with obvious photochromic effect. Compared to the wild type BR, the lifetime of M state of BR-D96N is prolonged to several minutes so that the photochromic kinetics and the intermediates formation can be studied by the conventional spectra analysis. In the experiment, the absorption spectra of the sample at different time after light illumination are measured with spectrophotometer. By fitting and analyzing the variation of the spectra, we suppose there-are three main states in the photochromic process, i.e. B state (light-adapted state), M state and D state (dark-adapted state). The absorption spectra of the B state, M state and D state are extracted from the experimental data based on this three-state model and the spectra at various time are fitted With the least square method. So, the variations of population percentages of the M state, B state and D state are obtained and the M state and B state lifetimes are estimated. In another,way, from measuring the absorption dynamics at 407 nm and 568 nm, the M state and B state lifetimes are also obtained by two exponential data fitting, which give coincident results with those of the spectra analysis.

Kinetic Studies of Gas Flows

Our recent studies on kinetic behaviors of gas flows are reviewed in this paper. These flows have a wide range of background, but share a common feature that the flow Knudsen number is larger than 0.01. Thus kinetic approaches such as the direct simulation Monte Carlo method are required for their description. In the past few years, we studied several micro/nano-scale flows by developing novel particle simulation approach, and investigated the flows in low-pressure chambers and at high altitude. In addition, the microscopic behaviors of a couple of classical flow problems were analyzed, which shows the potential for kinetic approaches to reveal the microscopic mechanism of gas flows.

Kinetic analysis of interaction between lipopolysaccharide and biomolecules

Lipopolysaccharide ( LPS) is a major component of the outer membrane of all gram-negative bacteria. It is a heat-resistant toxin which can cause toxic shock in animals. LPS interacts with some biomolecules and triggers its toxic reaction. In this study, the interaction between LPS from Salmonella Minnesota and some biomolecules using syrface okasnib resibabce ( SPR) biosensor. biomolecules were imobilized on CM5 sensor-chip suing amion coupling method and LPS was injected over the immobilized surfaces.

Kinetic study of DNA/DNA hybridization with electrochemical impedance spectroscopy

The hybridization of immobilized oligonucleotides probe strands with solution phase targets is the underlying principle of microarraybased techniques for the analysis of DNA variation. To study the kinetics of DNA/DNA hybridization, target DNA is often prior labeled with markers. A label-free method of electrochemical impedance spectra (EIS) for study the hybridization in process was reported. The Langmuir model was used to determine the association rate constant (K-on), the dissociation rate constant (K-off) and the affinity rate constant (K-A), for perfect matched DNA hybridization. The results show that, EIS is a successful technique possessing high effectivity and sensitivity to study DNA/DNA hybridization kinetics. This work can provide another view on EIS for the studying of DNA/DNA hybridization.

Deposition of GdVO4 : Eu3+ nanoparticles on silica nanospheres by a simple sol-gel method

The deposition and coating of GdVO4: Eu3+ nanoparticles on spherical silica was carried out using a simple sol - gel method at low temperature. The GdVO4: Eu3+-coated silica composites obtained were characterized by differential thermal analysis (DTA), thermogravimetric (TG) analysis, x-ray diffraction (XRD), Fourier-transform IR spectroscopy (FT-IR), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), photoluminescence spectra, and kinetic decay. It is found that the similar to 5 nm GdVO4: Eu3+ nanoparticles coating the silica spheres are crystal in the as-prepared samples and the crystallinity increases with increasing annealing temperature. The composites obtained are spherical in shape with an average size of 100 nm. The GdVO4: Eu3+ nanoparticles are linked with silica cores by a chemical bond. The photoluminescence spectra of the obtained GdVO4: Eu3+-coated silica composites are similar to those of the bulk GdVO4: Eu3+ phosphors. The strongest peak is near 617 nm, which indicates that Eu3+ is located in the low symmetry site with non-inversion centre.

Morphology and structure of poly(di-n-butylsilane) single crystals prepared by controlling kinetic process of solvent evaporation

The silicon backbone conformation in poly(di-n-butylsilane) (PDBS) has been shown to be a 7/3 helix at ambient conditions, which is in marked contrast to the near-planar conformation of its homologous polymers with side chain lengths of one to three or six to eight carbon atoms. In this work, both the 7/3 helical and near-planar chain conformations are achieved by controlling the solvent evaporation rate around room temperature. The chain conformation and crystal structure obtained in this method have been correlated to the crystal morphology by wide-angle X-ray diffraction, transmission electron microscopy, electron diffraction, optical microscopy, atomic force microscopy, and UV absorption spectrum. The lath-shaped single crystals obtained at 12 degreesC correspond to an orthorhombic form with near-planar chain conformation whereas the lozenge-shaped single crystals obtained at 30 degreesC (in coexistence with the lath-shaped crystals) are orthohexagonal with a 7/3 helix.

Fabrication of a metalloporphyrin - Polyoxometalate hybrid film by a layer-by-layer method and its catalysis for hydrogen evolution and dioxygen reduction

Tetrakis (N-methylpyridyl) porphyrinato] cobalt (CoTMPyP) and 1:12 silicotungstic acid (SiW12) were alternately deposited on a 4-aminobenzoic acid (4-ABA)-modified glassy carbon electrode through a layer-by-layer method. The resulting organic-inorganic hybrid films were characterized by cyclic voltammetry (CV) and UV/vis absorption spectroscopy. We proved that the prepared multilayer films are uniform and stable. SiW12-containing multilayer films (SiW12 as the outermost layer) exhibit remarkable electrocatalytic activity for the hydrogen evolution reaction (HER). The kinetic constants for HER were comparatively investigated at different layers Of SiW12/CoTMPyP multilayer film-modified electrodes by hydrogen evolution voltammetry. In addition, rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) voltammetric methods confirm that SiW12/CoTMPyP (CoTMPyP as the outermost layer) multilayer films catalyze almost a two-electron reduction of O-2 to H2O2 in pH 1-6 buffer solutions. Furthermore, P2W18/CoTMPyP films were also assembled, and their catalytic activity for HER is very different from that Of SiW12/CoTMPyP multilayer films.