Improved voltage transfer coefficients for nonconductive materials in radiofrequency glow discharge optical emission spectrometry

In radiofrequency glow discharge emission spectrometry (RF-GDOES), the excitation voltage used to create the plasma is applied to the back or front end of the sample to be analyzed. In this paper we focus on back-applied voltage systems (a configuration that represents about half of the instruments available on the market), and on applied voltage problems (the power coupling efficiency and materials analysis are beyond the scope of this study). In the RF-GDOES of nonconductive samples, a voltage drop develops inside the material. The voltage transfer coefficient is defined as the ratio between the peak voltage in front of the sample (facing the plasma) and the peak voltage applied to the back of the sample. In this work, we show that it is possible to increase the voltage transfer coefficient by increasing the capacitance of the sample. The capacitance of a given nonconductive material depends on its surface, its thickness and its permittivity. Increasing the voltage transfer coefficient permits higher power deposition in the plasma. This study is based on an electrical equivalent circuit for the discharge device, which takes into account the sample and reactor capacitances as well as the voltage probes used for the measurements. This circuit, when modeled by a commercial electrical circuit simulator, gives the voltage transfer coefficient as a function of the sample capacitance. Different approaches to increasing the sample capacitance and their influence on the voltage transfer coefficient are presented and related to the 750.4 nm argon line intensity, which is correlated to the electron density.     

Unexpected role of electronic coupling between host redox centers in transport kinetics of lithium ions in olivine phosphate materials

The discrepancy between the trend in the diffusion coefficient of a lithium ion (D_Li⁺) and that in the activation energy of ion hopping signals hidden factors determining ion transport kinetics in layered olivine phosphate materials (LiMPO₄). Combining density functional theory (DFT) calculations and the Landau–Zener electron transfer theory, we unravel this hidden factor to be the electronic coupling between redox centers of the host materials. The ion transport process in LiMPO₄ is newly described as an ion-coupled electron transfer (ET) reaction, where the electronic coupling effect on D_Li⁺ is considered by incorporating the electronic transmission coefficient into the rate constant of the transfer reaction. The new model and DFT calculation results rationalize experimental values of D_Li⁺ for various LiMPO₄ (M = Fe, Mn, Co, Ni) materials, which cannot be understood solely by the calculated activation barrier of ion hopping. Interestingly, the electronic coupling between host redox centers is found to play an essential role. Particularly, the sluggish ion mobility in LiFePO₄ is due to a very weak electronic coupling. The obtained insights imply that one can improve the rate performance of intercalation materials for metal-ion batteries through modifying the electronic coupling between redox centers of host materials.

The discrepancy between the trend in the diffusion coefficient of lithium ions (D_Li⁺) and that in the activation energy of ion hopping signals hidden factors determining ion transport kinetics in layered olivine phosphate materials (LiMPO₄).     

Electroreduction of 6-amino-5-nitroso-1,3-dimethyluracil on polycrystalline platinum and nickel cathodes in acid aqueous solution

The reduction of 6-amino-5-nitroso-1,3-dimethyluracil (ANDMU) is a key step in caffeine synthesis. Electroreduction technology is a promising green chemical process. The voltammetric behavior of ANDMU at polycrystalline platinum and nickel cathodes was studied. The Nicholson theory was used to resolve the reduction process semi-quantitatively. The results show that ANDMU mainly undergoes an ECE (electron transfer, chemical reaction, electron transfer) process involving four electrons on the platinum and nickel cathodes in which the two electron-transfer steps occur at almost the same potential and the rate of the coupling chemical reaction between two electron-transfer steps is very fast. Apparent kinetic data and diffusion coefficient were determined for the platinum rotating-disk electrode.     

"Almost delocalized" intervalence compounds

Interest is high in +M-bridge-M systems that have very low barriers to intramolecular electron transfer giving M-bridge-M+ ("almost delocalized" systems). Hush showed how to evaluate the electronic coupling across the bridge (H) from the M-to-M charge-transfer optical absorption band, but did not point out that his classical model causes the extinction coefficient to suddenly drop to zero at a photon energy of 2 H. Ignoring this band cutoff leads to a low estimation of H.     

Coupling between protein and reaction dynamics in enzymatic processes: application of Grote-Hynes Theory to catechol O-methyltransferase

The generalized Langevin equation (GLE)-based Grote-Hynes (GH) theory is used to calculate the transmission coefficients, kappa, for the methyl transfer from S-adenosylmethionine to catecholate both in aqueous solution and in the catechol O-methyltransferase active site. Values of kappa, which measures the deviation of the rate constants from the Transition State Theory (TST) predictions, are obtained by means of rare event molecular dynamics simulations. The results are 0.62 +/- 0.04 and 0.83 +/- 0.03 for the aqueous and enzymatic environments, respectively, while the Grote-Hynes predictions are 0.58 +/- 0.09 and 0.89 +/- 0.03, respectively. The Kramers theory estimates are much smaller, about 0.01 and 0.1, respectively. Thus, the enzymatic transmission coefficient is closer to TST predictions than the value obtained in solution. In addition, our results show that the enzymatic coefficient is also closer to its nonadiabatic (or frozen environment) limit than is the solution coefficient. These findings can be understood considering that, during the passage over the barrier top, there is a smaller coupling between the reactive system and the environment in the enzyme than in solution, as well as a smaller reorganization suffered by the enzyme. Analysis of the transition state friction kernel leads to the identification of some key vibrational modes governing the coupling between the two different environments and the reacting solute in the transition state region and insights on their relevance for the reaction dynamics' influence on the transmission coefficient.     

Phenomenological study on heat and mass coupling mechanism of waxy crude oil pipeline transport process

Based on the phase equilibrium model of the paraffin wax precipitation in the process of oil pipeline transportation, theory and method of non-equilibrium thermodynamics were applied to obtain the linear phenomenological equations for the cross-interaction of heat and mass transfer during pipeline transport, which were derived from the irreversible entropy production rate equation. Then, the analysis of the irreversible heat flow and the mass flow were carried out, and the mathematical expressions of the phenomenological coefficient of liquid phase, the phenomenological coefficient of solid phase flow, and the heat flow phenomenological coefficient were obtained. Taking a waxy crude oil transportation pipeline in Daqing Oilfield as an example, based on the analysis of liquid–solid phase equilibrium, the irreversible linear phenomenological mechanism of heat and mass coupling in waxy crude oil pipeline transportation was analyzed in detail from three levels: phenomenological coefficients which reflect characteristic of the effect of force on flow in heat and mass transfer; thermodynamic forces which trigger heat and mass transfer; transmitted heat and mass flow density, providing a theoretical basis for the further study of the wax deposition in the process of pipeline transportation.     

粘结超磁致伸缩Tb-Dy-Fe合金磁致伸缩性能的研究

采用粘结方法制备了Tb1-xDyxFe2棒状合金样品，经筛选确定了粘结材料的制备工艺，测试了粘结棒状合金样品的静态、动态磁致伸缩系数和磁机械耦合系数k33。结果表明，所制备的粘结棒状样品具有较高的磁致伸缩性能，且动态磁致伸缩参数k33和磁机械耦合系数k33高于国外所报道的结果。     

Theoretical studies of electron transfer through dendrimeric architecture

We have analyzed the steady-state electron transfer rate through a bridge of dendrimeric architecture. The difference between the linear chain and the dendrimeric architecture has also been demonstrated with steady-state rate as a main observable in the coherent and incoherent regimes of interactions. It is shown that generally the rate of electron transfer in dendrimeric architecture is faster than the rate associated with their linear chain counterpart with similar kind of bonding connectivities. The rate depends upon the size of the molecule, core branching, and the nature of the coupling among the different nodes on the dendrimer molecule. Depending upon the nature of the donor and acceptor, phenomenological dephasing coefficient due to environment and the geometry of the dendrimeric architecture, the modification of electron transfer rate has been studied. In the regime of fully coherent interactions where all quantum effects are considered the rate shows a multiple inversion due to the dendrimer architecture which is neither available in the regime of incoherent interaction nor in the linear chain case in similar condition. We have discussed about the applicability of our model in metal-molecule-metal junction, photoinduced electron transfer process, and molecular conductor.     

Emission band shape probes of the mixed-valence excited state properties of polypyridyl-bridged bis-ruthenium(II) complexes

The absorption spectra and emission spectral band shapes of several polypyridine-ligand (PP) bridged bis-ruthenium(II) complexes imply that the Ru(II)/Ru(III) electronic coupling is weak in their lowest energy metal to ligand charge transfer (MLCT) excited states. Many of these PP-bridging ligands contain pyrazine moieties and the weak electronic coupling of the excited states contrasts to the strong electronic coupling inferred for the correlated mixed-valence ground states. Although the bimetallic complexes emit at significantly lower energy than their monometallic analogs, the vibronic contributions to their 77 K emission spectra are much stronger than expected based on comparison to the monometallic analogs (around twofold in some complexes) and this feature is characteristic of bimetallic complexes in which the mixed-valence excited states are electronically localized. The weaker excited state than ground state donor/acceptor electronic coupling in this class of complexes is attributed to PP-mediated super-exchange coupling in which the mediating orbital of the bridging ligand (PP-LUMO) is partly occupied in the MLCT excited states, but is unoccupied in the ground states; therefore, the vertical Ru(III)-PP⁻ (MLCT) energy is larger and the mixing coefficient smaller in these excited states than is found for Ru(II)-PP in the corresponding ground states.     

Semiclassical treatment of thermally activated electron transfer in the intermediate to strong electronic coupling regime under the fast dielectric relaxation

The generalized nonadiabatic transition-state theory (NA-TST) (Zhao, Y.; et al. J. Chem. Phys. 2004, 121, 8854) is used to study electron transfer with use of the Zhu-Nakamura (ZN) formulas of nonadiabatic transition in the case of fast dielectric relaxation. The rate constant is expressed as a product of the well-known Marcus formula and a coefficient which represents the correction due to the strong electronic coupling. In the case of general multidimensional systems, the Monte Carlo approach is utilized to evaluate the rate by taking into account the multidimensionality of the crossing seam surface. Numerical demonstration is made by using a model system of a collection of harmonic oscillators in the Marcus normal region. The results are naturally coincident with the perturbation theory in the weak electronic coupling limit; while in the intermediate to strong electronic coupling regime where the perturbation theory breaks down the present results are in good agreement with those from the quantum mechanical flux-flux correlation function within the model of effective one-dimensional mode.     

Film Mass Transfer Coefficient Expressions for Electroosmotic Flows

Expressions are developed and presented that could be used to determine the film mass transfer coefficient of a solute in electroosmotic flows. In contrast to pressure-driven flows at low Reynolds numbers where the film mass transfer coefficient is independent of the linear characteristic dimension of the channel for flow, in electroosmotically driven flows at low Reynolds numbers the film mass transfer coefficient is shown to be a function of the ratio R/lambda, where R is the channel radius and lambda is the Debye length. This result implies that for electroosmotically driven flows in a packed bed or porous monolith with channels for flow having similar geometry but different sizes, the film mass transfer coefficient would vary with the size of the interstitial channels for bulk flow while in pressure-driven flows the film mass transfer coefficient would be the same for all interstitial channels. From the expressions presented in this work, one can show that for the same volumetric flow rate the film mass transfer coefficient of electroosmotically driven flows is proportional to that for pressure-driven flows. Copyright 2000 Academic Press.     

Nonlinear coupling in the quantum statistical theory of proton transfer dynamics

The possible role of the nonlinear coupling on the character of the dynamics of particle transfer process is investigated. The analysis and solutions of the kinetic equation indicate that nonlinear coupling causes symmetry breaking of particle transfer potential and determines possible equilibrium structure of the system. Dissipative coupling characterizes the rate of the system to reach thermodynamic equilibrium and along with nonlinear coupling and parameters of the system determines in a unique way the resulting equilibrium structure of the system.     

化学自催化混沌反应模型中的耦合作用与混沌同步

选用混沌自催化反应作为子系统,构造了耦合自催化反应系统,研究了耦合变量、耦合系数对混沌动力学行为的影响,给出了不同耦合系数下系统的动力学特征,探讨了耦合作用机制.结果表明,耦合作用能明显地改变子系统的动力学行为,强化系统间的相关性.耦合后的混沌运动受到调整与抑制,耦合强度加大时,呈现出混沌运动轨线的周期化,耦合系数大于临界值,两子系统实现了完全的同步.不同变量的耦合时,影响最大的是第二种变量.对于三种物质均有耦合时,更容易出现混沌的抑制、运动状态的锁相与周期化和混沌的完全同步.     

Effects of Configurational Fluctuation on Electronic Coupling for Charge Transfer Dynamics

We advance a theory for the effects of bridge configurational fluctuations on the electronic coupling for electron transfer reactions in donor-bridge-acceptor systems. The theory of radiationless transitions was applied for activationless electron transfer, where the nuclear Franck–Condon constraints are minimized, with the initial vibronic state interacting directly with the final vibronic manifold, without the need for thermal activation. Invoking the assumption of energy-independent coupling, the time-dependent initial state population probability was analyzed in terms of a cumulant expansion. Two limiting situations were distinguished, i.e. the fast configurational fluctuation limit, where the electron transfer rate is given in terms of the configurational average of me squared electronic coupling, and the slow configurational fluctuation limit, where the dynamics is determined by a configurational averaging over a static distribution of electron transfer probability densities. The correlation times for configurational fluctuations of the electronic coupling will be obtained from the analysis of molecular dynamics, in conjunction with quantum mechanical calculations of the electronic coupling, to establish the appropriate limit for electron transfer dynamics.     

Synthesis and properties of polysiloxane-based electrooptic materials

In this study, new functionalized polysiloxane material was synthesized. The polysiloxane-based electrooptic material with side-chain charge-transporting functionalities and nonlinear optical chromophores was investigated through a three-step synthetic route. Elementary analysis and NMR spectra indicate that the polymer has a high degree of substitution. Detailed physical properties showed that the polymer has a glass transition of around 91°C, and its photoconductivity and electrooptic coefficient increase with the increasing applied electric field. Photorefractivity of the system has been demonstrated through the asymmetric energy transfer in a two-beam coupling experiment. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3854–3860, 1999     

Electronic coupling matrix elements from charge constrained density functional theory calculations using a plane wave basis set

We present a plane wave basis set implementation for the calculation of electronic coupling matrix elements of electron transfer reactions within the framework of constrained density functional theory (CDFT). Following the work of Wu and Van Voorhis [J. Chem. Phys. 125, 164105 (2006)], the diabatic wavefunctions are approximated by the Kohn-Sham determinants obtained from CDFT calculations, and the coupling matrix element calculated by an efficient integration scheme. Our results for intermolecular electron transfer in small systems agree very well with high-level ab initio calculations based on generalized Mulliken-Hush theory, and with previous local basis set CDFT calculations. The effect of thermal fluctuations on the coupling matrix element is demonstrated for intramolecular electron transfer in the tetrathiafulvalene-diquinone (Q-TTF-Q(-)) anion. Sampling the electronic coupling along density functional based molecular dynamics trajectories, we find that thermal fluctuations, in particular the slow bending motion of the molecule, can lead to changes in the instantaneous electron transfer rate by more than an order of magnitude. The thermal average, (<|H(ab)|(2)>)(1/2)=6.7 mH, is significantly higher than the value obtained for the minimum energy structure, |H(ab)|=3.8 mH. While CDFT in combination with generalized gradient approximation (GGA) functionals describes the intermolecular electron transfer in the studied systems well, exact exchange is required for Q-TTF-Q(-) in order to obtain coupling matrix elements in agreement with experiment (3.9 mH). The implementation presented opens up the possibility to compute electronic coupling matrix elements for extended systems where donor, acceptor, and the environment are treated at the quantum mechanical (QM) level.     

Dynamic nature of the intramolecular electronic coupling mediated by a solvent molecule: a computational study

We present a combined Molecular Dynamics/Quantum Chemical study of the solvent-mediated electronic coupling between an electron donor and acceptor in a C-clamp molecule. We characterize the coupling fluctuations due to the solvent motion for different solvents (acetonitrile, benzene, 1,3-diisopropyl-benzene) for the charge separation and the charge recombination processes. The time scale for solvent-induced coupling fluctuation is approximately 0.1 ps. The effect of these fluctuations on the observed rate is discussed using a recently developed theoretical model. We show that, while the microscopic charge transfer process is very complicated and its computational modeling very subtle, the macroscopic phenomenology can be captured by the standard models. Analyzing the contribution to the coupling given by different solvent orbitals, we find that many solvent orbitals mediate the electron transfer and that paths through different solvent orbitals can interfere constructively or destructively. A relatively small subset of substrate-solvent configurations dominate contributions to solvent-mediated coupling. This subset of configurations is related to the electronic structure of the C-clamp molecule.