Macroscopic theory of electrochemical transducer of alternating current,based on two-dimensional model with mesh cathodes

Basing on approximate equations describing real processes, a possibility of the presenting in general closed form of the theoretical frequency dependence of diffusion current density in the entire frequency range is considered.     

Vibrational spectral diffusion of azide in water

Vibrational spectral diffusion denotes the time-dependent fluctuations of a solute's vibrational frequencies due to local environmental dynamics. Vibrational line shapes are weakly sensitive to spectral diffusion, whereas three-pulse vibrational echoes are much more sensitive. We report here on theoretical studies of spectral diffusion of the asymmetric stretch of the azide anion in heavy water. We run a classical molecular dynamics simulation of rigid azide in rigid water, and at every time step we calculate the azide's anharmonic asymmetric stretch frequency using an optimized quantum mechanics/molecular mechanics method developed earlier. This generates a frequency trajectory, which we use to calculate the absorption line shape and integrated three-pulse echo intensity. Our results for both the line width and the integrated echo intensity are in excellent agreement with experiment. Our calculated frequency time-correlation function is in excellent agreement with experiment for long times (greater than 250 fs) but differs considerably from experiment at short times; our theoretical correlation function has a very pronounced oscillation, presumably due to intermolecular azide-water hydrogen-bond stretching dynamics.     

A first principles simulation study of fluctuations of hydrogen bonds and vibrational frequencies of water at liquid-vapor interface

We present a theoretical study of the structure and dynamics of water-vapor interface by means of ab initio molecular dynamics simulations. The inhomogeneous density, hydrogen bond and orientational profiles, voids and vibrational frequency distributions are investigated. We have also studied various dynamical properties of the interface such as diffusion, orientational relaxation, hydrogen bond dynamics and vibrational frequency fluctuations. The diffusion and orientational relaxation of water molecules are found to be faster at the interface which can be correlated with the voids present in the system. The hydrogen bond dynamics, however, is found to be slightly slower at the interface than that in bulk water. The correlations of hydrogen bond relaxation with the dynamics of vibrational frequency fluctuations are also discussed.     

Kinetics of Adsorption of Neutral Molecules from a Thin Layer on a Rough Electrode

A theoretical model for the generalized finite adsorption impedance of a rough electrode is offered. A complex function of the roughness of the electrode surface is introduced and its frequency dependence is studied. The frequency characteristics of constituents of the adsorption impedance are shown to depend on the electrode roughness and the diffusion layer thickness. The frequency dependences of the phase angle and impedance components are found to considerably differ from the Frumkin–Melik-Gaikazyan result for an ideal smooth electrode.     

Measuring Ultrafast Spectral Diffusion and Correlation Dynamics by Two‐Dimensional Electronic Spectroscopy

The frequency fluctuation correlation function (FFCF) measures the spectral diffusion of a state's transition while the frequency fluctuation cross‐correlation function (FXCF) measures the correlation dynamics between the transitions of two separate states. These quantities contain a wealth of information on how the chromophores or excitonic states interact and couple with its environment and with each other. We summarize the experimental implementations and theoretical considerations of using two‐dimensional electronic spectroscopy to characterize FFCFs and FXCFs. Applications can be found in systems such as the chlorophyll pigment molecules in light‐harvesting complexes and CdSe nanomaterials.     

Use of Nonlinear Frequency Response for Discriminating Adsorption Kinetics Mechanisms Resulting with Bimodal Characteristic Functions

One of the characteristic examples of the inability of the classical linear frequency response (FR) method to identify the correct kinetic mechanism is adsorption of some substances (p-xylene, 2-butane, propane or n-hexane) on silicalite-1. The linear FR resulted with bimodal FR characteristic functions, which fitted equally well to three different kinetic models: nonisothermal micropore diffusion, two independent isothermal diffusion processes, and an isothermal diffusion-rearrangement process. We show that the second order frequency response functions (FRFs), obtained from the nonlinear FR, can be used for discrimination among these three mechanisms. Starting from the nonlinear models, we derive the theoretical expressions for the first and second order FRFs corresponding to these three mechanisms and show that different shapes of the second order FRFs are obtained for each mechanism. This would enable identification of the real mechanism from nonlinear FR data.     

非导电微球悬浊系的介电谱——弛豫机制的考察和界面信息的解析

研究了不同浓度电解质溶液中聚苯乙烯微球悬浊液的介电谱, 发现在40 Hz～110 MHz频率范围内出现了两个明显的弛豫. 在介电模型基础上对弛豫原因的理论分析结果表明, 千赫兹频域出现的弛豫是由粒子附近双电层中对离子的扩散所致, 兆赫兹附近出现的弛豫源于空间电荷在固/液界面的累积. 应用Hanai方法计算出体系内部的相参数, 获得了微球/溶液界面的电信息, 并给出了合理解释. 理论计算结果验证了模型和方法的适用性. 实验采用透析法调制样品, 有效地防止了体系内部粒子二次团聚的发生.     

Alternating‐Current Measurements in Scanning Electrochemical Microscopy,Part 1: Principle and Theory

The development of the scanning electrochemical microscope in ac mode is presented from both experimental and theoretical point of views. The experiments are performed with the ferri/ferrocyanide redox mediator as model system. Based on analysis of the frequency‐dependent collection efficiency, diffusion between the probe and the substrate is investigated, and analysis of time constants allows evaluation of the size of the sensing area under investigation. The experimental results are in good agreement with numerical simulations.     

Diffusion Impedance in Natural Convection Conditions

An expression for the diffusion impedance in conditions of natural convection, when the diffusion layer thickness depends on the redox pair concentration, is obtained. The theory predicts a decrease in the steady-state diffusion resistance R _dby 1.25 times and a change in the coordinates of the extremum in an impedance spectrum and in the dimensionless R _dfrequency at this point (3.2 instead of 2.5) as compared to the classical theory, which is confirmed by experimental data for a reversible [Fe(CN)₆]^3–/4–system. The theoretical results are employed for correct determination of the concentration coefficient of the solution density.     

Investigation of gas transport through porous membranes based on nonlinear frequency response analysis

Theoretical development of a new experimental method for investigation of mass transport in porous membranes, based on the principle of the modified Wicke-Kallenbach diffusion cell and the nonlinear frequency response analysis is presented. The method is developed to analyze the transport of a binary gas mixture in a porous membrane. The mixture is assumed to consist of one adsorbable and one inert component. Complex mass transfer mechanism in the membrane, where bulk or transition diffusion in the pore volume and surface diffusion take place in parallel, is assumed. Starting from the basic mathematical model equations and following a rather standardized procedure, the frequency response functions (FRFs) up to the second order are derived. Based on the derived FRFs, correlations between some characteristic features of these functions on one side, and the whole set of equilibrium and transport parameters of the system, on the other, are established. As the FRFs can be estimated directly from different harmonics of the measured outputs, these correlations give a complete theoretical basis for the proposed experimental method. The method is illustrated by quantifying the transport of helium (inert gas) and C₃H₈ and CO₂ (adsorbable gases) through a porous Vycor glass membrane.     

Vibrational spectral diffusion and hydrogen bond dynamics in heavy water from first principles

We present a first-principles theoretical study of vibrational spectral diffusion and hydrogen bond dynamics in heavy water without using any empirical model potentials. The calculations are based on ab initio molecular dynamics simulations for trajectory generation and a time series analysis using the wavelet method for frequency calculations. It is found that, in deuterated water, although a one-to-one relation does not exist between the instantaneous frequency of an OD bond and the distance of its associated hydrogen bond, such a relation does hold on average. The dynamics of spectral diffusion is investigated by means of frequency-time correlation and spectral hole dynamics calculations. Both of these functions are found to have a short-time decay with a time scale of approximately 100 fs corresponding to dynamics of intact hydrogen bonds and a slower long-time decay with a time constant of approximately 2 ps corresponding to lifetimes of hydrogen bonds. The connection of the slower time scale to the dynamics of local structural relaxation is also discussed. The dynamics of hydrogen bond making is shown to have a rather fast time scale of approximately 100 fs; hence, it can also contribute to the short-time dynamics of spectral diffusion. A damped oscillation is also found at around 150-200 fs, which is shown to have come from underdamped intermolecular vibrations of a hydrogen-bonded water pair. Such assignments are confirmed by independent calculations of power spectra of intermolecular motion and hydrogen bond kinetics using the population correlation function formalism. The details of the time constants of frequency correlations and spectral shifts are found to depend on the frequencies of chosen OD bonds and are analyzed in terms of the dynamics of hydrogen bonds of varying strengths and also of free non-hydrogen-bonded OD groups.     

Oscillations of the concentration during sorption of amino acids on ion exchanger grains

Low frequency oscillations of the concentration can arise in the process of diffusion and sorption of amino acids under the stationary external conditions. This phenomenon has been observed in some experimental works. In the present paper it is studied by means of modelling. The physical factors responsible for a positive feedback between variations of solution flow and changes in the concentration are found. These factors give rise to instability of the process and oscillations of the concentration. The theoretical explanation of the phenomenon and the results of calculations are presented in this paper.     

Tracer diffusion of Co2+ ions in agar gel containing multi-electrolyte systems

Tracer diffusion coefficients of cobalt ions have been measured in the supporting medium containing multi-electrolyte systems of alkali bromides. The electrolyte concentration was varied between 10^–6-0.1M at 25°C and the diffusion coefficients were determined by zone-diffusion technique using agar gel medium. The trend in the theoretical values of diffusion coefficients is accounted for by considering the relative contribution of mobility function, ionic strength as well as ion size parameter to the theoretical value in different systems. While the deviations between theoretical and experimental values of diffusion coefficients are explained on the basis of various co-occurring effects in ion-gel-water system.     

Effect of Adsorption of Neutral Molecules on the EDL Capacitance of a Rough Electrode

The perturbation theory is used to design a theoretical model for the Frumkin–Melik-Gaikazyan impedance of a sine electrode with a perturbation parameter equal to the ratio between the amplitude of surface oscillations and its period for a diffusion-controlled adsorption stage. The unequal diffusion access to the interface increases its capacitance. At higher frequencies, the electrode capacitance is defined by its geometric roughness factor. At lower frequencies, the capacitance depends on the adsorption conditions. The adsorption of electroactive substances results in a constant phase angle; the electrode roughness alters it and the frequency range where it remains constant.     

Determination of Bulk and Surface Diffusion Coefficients from Experimental Data for Thin Liquid Film Drainage

This note presents a method for the determination of the surface diffusion coefficient and surface diffusion flux. The theoretical considerations are based on the Onsager linear theory for the definition of the surface diffusion flux and on the Einstein theorem for the definition of the surface diffusion parameter. In this interpretation the surface diffusion coefficient differs from the one commonly defined in the literature. It does not depend on the surfactant concentration and it is a function only of the type of surfactant and the liquid/liquid interface. The theoretical calculations indicate that the effect of the surface diffusion on the film drainage is stronger than that predicted by previous theoretical studies. The experimental data for thin liquid film drainage in the case of low surfactant concentration in the continuous phase could be used for the calculation of the bulk and surface diffusion coefficients. In the present study we utilized the experimental data for the drainage of nitrobenzene films stabilized by different concentrations of dodecanol. Copyright 2000 Academic Press.     

Mutual-diffusion of some transition metal halides

The diffusion of some zinc and cobalt salts in water have been measured using an improved version of the capillary technique. In this technique, diffusion proceeds in the absence of stirring in the bulk solution. The amount of diffusing substance which remains in the capillary is analyzed after a chosen time. Nanis' solution for three-dimensional diffusion from a capillary has been used to calculate the experimental values. The values of diffusion coefficient of zinc iodide, cobalt bromide and cobalt iodide have been obtained with a diffusion run time of four hours. A comparison has been made between the experimental and theoretical values obtained from Onsager-Fuoss theory. An attempt has also been made to explain the deviation between the experimental and theoretical values over the concentration range studied.     

Study of mass transfer in a dynamic hollow‐fibre liquid phase microextraction system

The extraction characteristics of a dynamic hollow‐fibre liquid phase microextraction system were investigated by studying the mass transfer and diffusion rates of dinitrophenols from plasma samples over the liquid membrane (dihexylether). The measured diffusion coefficients were compared with theoretical values calculated from Stokes diameters. The diffusion mechanism was simulated by computer and the most polar compounds, 2,4‐dinitrophenol and 4,6‐o‐dinitrocresol, had associated diffusion coefficients that were close to the calculated theoretical values. 2‐sec‐Butyl‐4,6 dinitrophenol and 2‐tert‐butyl‐4,6‐dinitrophenol, the compounds with the highest log P values, were retained by the polypropylene membrane, which reduced the experimentally observed diffusion rates to about half of the theoretical values. The retention was most likely due to dispersive forces interacting with the pore inner walls. Extraction was linearly correlated with time for all compounds and the repeatability was high (RSDs 7–11%), even for the shortest extraction times. Method LOD as the amount injected ranged between 0.3 and 3.1 ng for an extraction cycle of 213 s.     

Processes of mass transfer of low-molecular-weight liquids in crosslinked elastomers

Experimental and theoretical works devoted to the study of diffusion phenomena of the transfer of plasticizers and organic solvents in polymeric materials are reviewed. Current theoretical models describing diffusion processes in deformed solids and polymeric materials are analyzed from the viewpoint of their ability to describe the transfer of plasticizers in elastomers. Current notions of mass transfer processes in crosslinked elastomers are supplemented by results obtained in recent years.     

Phase-response characteristics of the transfer function of a spatially limited electrochemical cell

Investigation of the dynamic characteristics of diffusion transducers is of great practical importance because of the wide utility of these devices in instruments for measuring the movement parameters and wave fields. Previously, cathode currents were the object of investigation because their difference was used as an output signal in several useful devices. In this work we investigated the amplitude and phase relationships between currents measured on both cathodes and anodes over a wide range of frequencies in a four-electrode electrochemical cell. It was shown in experiment that the sum of the currents recorded on the four electrodes of a molecular electronic cell (MEC) is zero, as follows from the condition of conservation of an electric charge. At frequencies as low as ～0.1 Hz the frequencies of the signal currents of the anode and the nearest cathode coincided. As the frequency grew to f ～80 Hz, the phase difference monotonously increased to values close to π. Previous theoretical models suggested, explicitly or implicitly, that the phases of the signal currents coincided over the whole range of frequencies in each anode-cathode pair. The results of the experiment were explained within the framework of the theoretical model of a four-electrode electrochemical cell, which is based on the one-dimensional equation of convective diffusion and takes into account the limited space of the cell.