Characterization of electrical charge separation at the interface of two aqueous solutions in the presence of concentration gradients and cation/anion mobility ratio asymmetry

Physical consequences of ionic diffusion processes play a major role on the outcome of electrophysiology experiments due to both their contribution to the ionic transmembrane transport and phenomena taking place at the measuring instruments interface. As most of the time heterogenities in biological media with respect to ionic diffusion constants are disregarded, we intended to look upon the general case of ionic diffusion at the interface of two liquids on which gradients of these diffusion constants no longer can be neglected. We developed a theoretical model for the diffusion potential which emerges at an aqueous interface under gradients of concentration and diffusion constants. The experimental validation of our model was achieved through potential difference measurements of the diffusion potential between two solutions containing sodium chloride (NaCl) and glycerine solutions of various concentrations. Within the studied domain of the electrical charge mobility ratio, we noticed that experimental results are in agreement with the theoretically inferred diffusion potential values. This demonstrates that the resulting relationship for the diffusion potential inferred from our model could be applied for other cases, as well. When the ionic solutions contains an indefinite quantity of glycerine or an unknown substance able to modify diffusion constants of sodium and chloride, it was shown that through measurements of the diffusion potential one can infer the unknown concentration of glycerine and the modified ionic mobility ratio. This, in turn, builds up the foundation for a novel yet simple and efficient analitycal sensing device for quantitative determination in the field.     

Mode-coupling theory for purely diffusive systems

A mode-coupling formalism is developed for multicomponent systems of particles performing diffusive motion in a uniform host medium. The mode-coupling equations are derived from a set of nonlinear fluctuating diffusion equations by expanding the concentration-dependent diffusion constants about their equilibrium values. From the mode-coupling equations the dominant long time behavior of current-current and super-Burnett correlation functions is derived. As specific applications I consider the long time behaviors of these correlation functions for collective and tracer diffusion in a one-component lattice gas with particle-conserving stochastic dynamics. The results agree with those from exactly solvable models and computer simulations.     

Diffusion-induced instability in chemically reacting systems: Steady-state multiplicity,oscillation, and chaos

The dynamical behavior of two coupled cells or reactors is described. The cells are coupled by diffusion, e.g., through a semipermeable membrane, and the chemical reactions and initial or feed concentrations of all species are the same in the two cells. Each cell has only a single stable steady state in the absence of coupling, and the coupled system may exhibit multiple steady states, periodic oscillation, or chaos. The attractors of the coupled system may be either homogeneous (the two cells have equal concentrations) or inhomogeneous. Three two-variable kinetic models are examined: the Brusselator, a model of the chlorine dioxide-iodine-malonic acid reaction, and the Degn-Harrison model. The dynamical behavior of the coupled system is determined by the nonlinearities in the uncoupled subsystems and by two ratios, that of the diffusion constants of the two species and that of the area of the membrane to the product of the membrane thickness and the volume of a cell.     

Predicted diffusion rates on fcc (001) metal surfaces for adsorbate/substrate combinations of Ni, Cu, Rh, Pd, Ag, Pt, Au

We investigate the diffusion of a single metal atom on the surface of a fcc (001) metal. Two points concerning the application of kinetic models to diffusion were considered. First, we test the assumption of kinetic models that diffusion occurs via a sequence of uncorrelated jumps. Second, when kinetic models are applicable we predict reasonable values of the kinetic rate constants.

Direct molecular dynamics (MD) simulations were performed for Ag on Ag(001) and Rh on Rh(001) systems. Diffusion was found to obey an Arrhenius-type dependence on temperature in both systems. The barriers and prefactors extracted from the MD results agree with estimates made from transition state theory (TST) and the experimental values for the Rh system. We conclude that kinetic models are applicable to diffusion on fcc (001) surfaces.

Transition state theory was then used to estimate diffusion parameters for all other adsorbate/ substrate combinations of the metals Ni, Cu, Rh, Pd, Ag, Pt, and Au. These results indicate that the characteristics of diffusion are primarily a property of the adsorbate. We also predict Ag atoms to have an anomalously low diffusion barrier on all of the substrates in this study. We use the accurate many-body density functional based MD/MC-CEM potential energy surface which allows us to consistently treat these multi-component systems.     

Determination of the diffusion and viscosity coefficients from the properties of dual fluorescence of molecules in solutions

We have proposed and substantiated an approach that makes it possible to determine the diffusion and microviscosity coefficients in solutions from characteristics of the dual fluorescence of molecular probes. This approach uses the Stern-Volmer constants obtained upon fluorescence dynamic quenching in solutions. The relations that follow from the balance equations in terms of the formalism of two-level reactions in the excited state for the case of photoreactions of the kinetic character yield the dependences of the intensity ratio of the fluorescence bands of the normal form and tautomer on the degree of quenching. In accordance with these dependences, the dynamic quenching of the diffusion character (including the temperature quenching) changes the intensity distribution, and, based on these dependences, the Stern-Volmer constants and the bimolecular quenching constants can be determined, from which, using appropriate models, the diffusion and viscosity coefficients can be found. The merit of the method is its simplicity and availability, since it is based on the use of the data of steady-state measurements of fluorescence spectra with widespread standard instruments.     

Thermophysical properties and collision-induced light scattering as a probe for gaseous helium interatomic potentials

Isotropic and anisotropic collision-induced light scattering spectra of helium gas at room temperature 294.5?K and at 99.6?K with the second pressure virial coefficients, second acoustic virial coefficients, viscosity and thermal conductivity have been used for deriving the empirical models of the pair-polarizability trace and anisotropy and the interaction potential. Theoretical zeroth and second moments of the binary spectra using various models for the pair-polarizabilities and interatomic potential are compared with the experimental values performed by Le Duff's group. In addition, third pressure virial coefficients, isotopic thermal factors, self diffusion coefficients, second virial dielectric constants and second Kerr coefficients calculated for these models are compared with experimental ones. The results show that these models are the most accurate models reported to date for this system.     

Rotational Diffusion in Prolate Symmetric top Molecules

A comparative analysis of theoretical and experimental rotational diffusion constants was performed for a series of liquid phase prolate symmetric top molecules. It was observed that the tumbling diffusion constants, D⊥, predicted by the extended Hynes-Kapral Weinberg (HKW) model were invariably in closer agreement with experiment than were values determined by the Hu-Zwanzig (HZ) slip model of molecular reorientation. The HKW theory also yielded superior estimates of D‖ for two -CCI³ rotors. However, the experimental spinning diffusion coefficients for methyl (-CD³) rotors were much closer to the slip (Free Rotor) limit.     

A Monte Carlo simulation of random surfaces

We use a previously proposed stochastic process and carry out Monte Carlo simulations for two models of random surfaces defined on hypercubic lattices. Tests are carried out in five dimensions. The critical coupling constants are estimated for both models. One of the models allows also results on its entropy.     

Double-spin-echo diffusion weighting with a modified eddy current adjustment

Magnetic field inhomogeneities like eddy current-related gradient fields cause geometric distortions in echo-planar imaging (EPI). This in particular affects diffusion-weighted imaging where these distortions vary with the direction of the diffusion weighting and hamper the accurate determination of diffusion parameters. The double-spin-echo preparation often used aims to reduce the cumulative eddy current effect by adjusting the diffusion-weighting gradient pulse durations to the time constant of the dominant eddy current contribution. However, eddy currents with a variety of time constants may be present and cause residual distortions. Here, a modification is proposed where the two bipolar gradient pairs of the preparation are adjusted independently to different time constants. At the expense of a slightly prolonged echo time, residual geometric distortions and correspondingly increased values of the diffusion anisotropy can be reduced as is demonstrated in phantoms and the human brain. Thus, it may help to improve the reliability of diffusion-weighted EPI.     

Surface exchange reactions and diffusion in composite materials: A finite element approach

A two-dimensional square grain model has been applied to model oxygen exchange processes between a gas phase and a ceramic composite consisting of two randomly distributed phases of equal grain size (side length of squares). Both average diffusion profiles for thin films and the time dependence of the total amount of exchanged oxygen (relaxation curves) have been calculated numerically by means of the finite element method. The boundary conditions refer to an instantaneous change of the oxygen partial pressure in the surrounding gas phase, which gives rise to surface exchange reactions as well as to diffusion in the composite. Both local equilibrium at the interface between different phases (host phase and inclusions) and blocking heterophase boundaries have been taken into account. The numerical results are compared with the analytical solution for diffusion in a homogeneous medium introducing effective diffusion and surface exchange coefficients. When the relaxation time for effective medium diffusion is considerably shorter than that for the transport process from the host phase into the inclusions, relaxation curves with two separate time constants are predicted. Based on analytical approximations, relaxation times for various limiting cases are given.     

Reactive diffusion in the Ti–Si system and the significance of the parabolic growth constant

Solid diffusion couple experiments are conducted to analyse the growth mechanism of the phases and the diffusion mechanism of the components in the Ti–Si system. The calculation of the parabolic growth constants and the integrated diffusion coefficients substantiates that the analysis is intrinsically prone to erroneous conclusions if it is based on just the parabolic growth constants determined for a multiphase interdiffusion zone. The location of the marker plane is detected based on the uniform grain morphology in the TiSi₂ phase, which indicates that this phase grows mainly because of Si diffusion. The growth mechanism of the phases and morphological evolution in the interdiffusion zone are explained with the help of imaginary diffusion couples. The activation enthalpies for the integrated diffusion coefficient of TiSi₂ and the Si tracer diffusion are calculated as 190 ± 9 and 197 ± 8?kJ/mol, respectively. The crystal structure, details on the nearest neighbours of the components, and their relative mobilities indicate that the vacancies are mainly present on the Si sublattice.     

Diffusion of tagged interacting spherically symmetric polymers

We consider the diffusion of two species of spherically symmetric macromolecules in solution under the influence of short range central pair potential interactions as well as two body hydrodynamic interactions. Starting from the N-particle Smoluchowski equation and using Felderhof's approach we derive, to linear order in densities, a pair of coupled diffusion equations for the single particle number densities. There are two independent diffusional modes each with an effective diffusion constant dependent in general upon both the interparticle potentials as well as the hydrodynamic model used for each type of macromolecule. However, in the limit that one species is present at very low density compared with the other species, one of the effective diffusion constants is dominated by hydrodynamic interactions. By tagging these tracer particles to observe their diffusion by light scattering, one can test both the mixed stick-slip boundary condition model and the permeable sphere model of the macromolecules.     

用NMR方法测定聚合物长侧基转动扩散系数

提出了一种测定聚合物溶液及有机固体中长侧基转动扩散系数的NMR方法,即先导出聚合物溶液和固体中长侧基运动的相关函数和谱密度函数,然后利用¹³C自旋弛豫数据求出扩散系数.同时还讨论了两个应用实例.     

Conformational dynamics of a metallomesogen studied by 2H-NMR spectroscopy

In this work we present a quantitative analysis of both quadrupolar splittings and deuterium Zeeman and quadrupolar spin-lattice relaxation times reported in the literature for two isotopomers of Azpac, an acetylacetonate derivative of the cyclopalladated 4, 4'-bis(hexyloxy) azoxybenzene. Azpac-d(4) is deuterated at the aromatic rings and Azpac-d(26) is deuterated on the alkoxy chains. The additive potential method is used to model the splittings, while the derived spectral densities are interpreted using the decoupled model in conjunction with the Nordio model. The two side chains are assumed to be noninteracting and identical in their conformations in order to limit the size of the transition rate matrix needed to describe correlated internal bond rotations in the chains. Rotational diffusion constants and internal jump rate constants are derived for this metallomesogen.     

Zur abschätzung des relaxationsbeitrages von internen bewegungen

Spin-lattice T1 and spin-spin T2 relaxation times of primary and tertiary amines were investigated by two different models (Woessner (a), Jardetzky (b)). It is shown that the internal diffusion constants D_i of the alkylchains can be well described by D^o_i and a formal rotational barrier. The overall correlation times determined from different independent T1 and T2 measurements are in excellent agreement. The weighted frequencies of motion λ_i of model (b) correlate to the D_i and D_o of model (a).     

Rate constants for the reaction of muonium with aromatic compounds

Rate constants for the reaction of muonium with benzene in water, methanol and n-hexane and for the reaction of muonium with p-difluorobenzene, anilin, hexafluorobenzene and styrene are reported. All rate constants are below the calculated diffusion controlled limit. The activation energy for the reaction of muonium with benzene in n-hexane is very small, indicating the possibility of tunnelling by muonium.     

Microscopic derivation of quantum fluctuations in nuclear reactions

The coupling between collective and intrinsic states of a nucleus is treated with first order time-dependent perturbation theory at zero temperature. In addition to the friction constant and conservative potential corrections, general expressions for the diffusion constants and differential equations in time for the second moments are derived for position and momentum dependent couplings, and are calculated in a particular solvable model. As a result, the diffusion constants do not necessarily vanish at zero temperature but there remain pure quantum effects. For oscillatory collective motion, the low temperature limit of the Einstein relation is given and an existence theorem for damped pure quantum states is derived.     

表面Cu原子间相互作用对Cu(001)表面跳跃扩散行为的影响

采用嵌入原子方法的原子间相互作用势，利用准静态分子动力学模拟研究了Cu原子在Cu(001)表面吸附所导致的基体晶格畸变以及对其附近的另一个吸附原子自扩散行为的影响.研究结果表明，吸附原子的存在可以导致多达10层的Cu基体晶格产生畸变.两个吸附原子所产生的晶格畸变应力场之间的相互作用，可以导致吸附原子运动活性的增加.通过比较同一路径上往返跳跃扩散势垒的差异发现，在原子间相互作用势的有效距离之外，两个吸附原子的扩散行为可以认为是存在晶格畸变应力场相互作用的两个独立吸附原子的扩散；在原子间相互作用势的有效距离之 关键词： 表面吸附原子 晶格畸变 表面二聚体 扩散     

Theory for the upper critical field in superconducting multilayers with interface irregularities

The upper critical field in superconducting multilayers, which are composed of two kinds of superconducting layers with different diffusion constants and contain interface irregularities, investigated in the direction parallel to the layers. The interface irregularities enhance the upper critical field. The crossover temperature at which the superconducting nucleation position moves from one layer to another is increased as the effect of the irregularities becomes strong. As a result, the two-dimensional region where the nucleation position of the superconducting order is inside a layer with the larger diffusion constant is greatly reduced by the irregularities.