Effects of phase-breaking on long-range charge transfer in DNA: Partially-coherent-tunneling model study

The mechanism of hole charge transfer in DNA of various lengths and sequences is investigated based on a partially coherent tunneling theory (Zhang et al., J Chem Phys 117:4578, 2002), where the effects of phase-breaking in adenine-thymine and guanine-cytosine base pairs are treated on equal foot. This work aims at providing a self-consistent microscopic interpretation for rate experiments on various DNA systems. We will also clarify the condition under which the simple superexchange-mediated-hopping picture is valid, and make some comments on the further development of present theory.

Interplay between partial incoherence, partial inelasticity, resonance, and heterogeneity in long-range electron transfer and transport

A generalized scattering matrix formalism is constructed to elucidate the interplay of electron resonance, coherence, dephasing, inelastic scattering, and heterogeneity, which play important roles in the physics of long-range electron transfer/transport. The theory consists of an extension of the standard Buttiker phase-breaking model and an analytical expression of the electron transmission coefficient for donor-bridge-acceptor systems with arbitrary length and sequence. The theory incorporates the following features: Dephasing-assisted off-resonance enhancement, inelasticity-induced turnover, resonance enhancement and its dephasing-induced suppression, dephasing-induced smooth superexchange-hopping transition, and heterogeneity effects. (C) 2002 American Institute of Physics.

Scattering matrix approach to electronic dephasing in long-range electron transfer

Based on the Buttiker dephasing model, we propose an analytical scattering matrix approach to the long-range electron transfer phenomena. The present efficient scheme smoothly interpolates between the superexchange and the sequential hopping mechanisms. Various properties such as the drastic dephasing-assisted enhancement and turnover behaviors are demonstrated in good agreement with those obtained via the dynamical reduced density-matrix methods. These properties are further elucidated as results of the interplay among the dephasing strength, the tunneling parameter, and the bridge length of the electron transfer system. (C) 2001 American Institute of Physics.

Golden-rule treatment on the ClO/ClO+ electron-transfer system

The structures, properties and electron transfer reactivity of the ClO/ClO+ coupling system are studied in this paper at ab initio (HF and MP2) levels and the density functional theory (DFT: B3LYP, B3P86, B3PW91) 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 got from the B3LYP method employing 6-311 + G(3df) basis set is in excellent agreement with the experiment. The activation energies, the stabilization energies and the electronic coupling matrix elements have also been calculated by using the B3LYP/6-311 + G(3df) method, and then the electron transfer rates are determined at this level. The electronic coupling matrix element of EC.6 is very small, only 0.03 kcal/mol, while that of EC.7 is the biggest, being 12.41 kcal/mol, the corresponding electron transfer rate is also the fastest among these seven encounter complexes. The averaged electron transfer rate is about 1.672 X 10(11) M-1 s(-1). It is indicated that the structures optimized by B3LYP method are more reliable than the results got from the other four methods. It also testified that the electronic coupling matrix element is the vital factor that significantly affects the electron transfer rate. (C) 2003 Elsevier B.V. All rights reserved.

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.

Investigation of facilitated ion-transfer reactions at high driving force by scanning electrochemical Microscopy

The kinetics of facilitated ion-transfer (FIT) reactions at high driving force across the water/1,2-dichloroethane (W/DCE) interface is investigated by scanning electrochemical microscopy (SECM). The transfers of lithium and sodium ions facilitated by dibenzo-18-crown-6 (DB18C6) across the polarized W/DCE interface are chosen as model systems because they have the largest potential range that can be controlled externally. By selecting the appropriate ratios of the reactant concentrations (Kr c(M)+/c(DB18C6)) and using nanopipets as the SECM tips, we obtained a series of rate constants (k(f)) at various driving forces (Delta(O)(W) phi(ML+)(0') - Es, Delta(O)(W) phi(ML+)(0') is the formal potential of facilitated ion transfer and Es is the potential applied externally at the substrate interface) based on a three-electrode system. The FIT rate constants k(f) are found to be dependent upon the driving force. When the driving force is low, the dependence of 1n k(f) on the driving force is linear with a transfer coefficient of about 0.3. It follows the classical Butler-Volmer theory and then reaches a maximum before it decreases again when we further increase the driving forces. This indicates that there exists an inverted region, and these behaviors have been explained by Marcus theory.

Effects of solution viscosity on heterogeneous electron transfer across a liquid/liquid interface

Scanning electrochemical microscopy (SECM) is employed to investigate the effect of solution viscosity on the rate constants of electron transfer (ET) reaction between potassium ferricyanide in water and 7,7,8,8-tetracyanoquinodimethane (TCNQ) in 1,2-dichloroethane. Either tetrabutylammonium (TBA(+)) or ClO4- is chosen as the common ion in both phases to control the interfacial potential drop. The rate constant of heterogeneous ET reaction between TCNQ and ferrocyanide produced in-situ, k(12), is evaluated by SECM and is inversely proportional to the viscosity of the aqueous solution and directly proportional to the diffusion coefficient of K4Fe(CN)(6) in water when the concentration of TCNQ in the DCE phase is in excess. The k(12) dependence on viscosity is explained in terms of the longitudinal relaxation time of the solution. The rate constant of the heterogeneous ET reaction between TCNQ and ferricyanide, k(21), is also obtained by SECM and these results cannot be explained by the same manner.

Systematic investigation of alkali metal ion transfer across the micro- and nano-water/1,2-dichloroethane interfaces facilitated by dibenzo-18-crown-6

Facilitated alkali metal ion (M+= Li+, Na+, K+, Rb+, and Cs+) transfers across the micro- and nano-water/1,2-dichloroethane (W/DCE) interfaces supported at the tips of micro- and nanopipets by dibenzo-18-crown-6 (DB18C6) have been investigated systematically using cyclic voltammetry. The theory developed by Matsuda et al. was applied to estimate the association constants of DB18C6 and M+ in the DCE phase based on the experimental voltammetric results. The kinetic measurements for alkali metal ion transfer across the W/DCE interface facilitated by DB18C6 were conducted using nanopipets or-submicropipets, and the standard rate constants (k(0)) were evaluated by analysis of the experimental voltammetric data. They increase in the following order: k(Cs+)(0) < k(Li+)(0) < k(Rb+)(0) < k(Na+)(0) < k(K+)(0), which is in accordance with their association constants except Cs+ and Li+.

Study of electron transfer across the liquid/ice-like matrix interface by scanning electrochemical microscopy

In this work, we report the findings of a study on scanning electrochemical microscopy (SECM) to investigate the interfacial electron-transfer (ET) reaction between the 7,7,8,8-tetracyanoquinodimethane radical anion (TCNQ(.-)) in 1,2-dichloroethane and ferricyanide in an ice-like matrix (a mixture of insulting ice and conductive liquid) under low temperatures. Experimental results indicate that the formed liquid/ice-like matrix interface is superficially similar in electrochemical characteristics to a liquid/liquid interface at temperatures above -20 degreesC. Furthermore, imaging data show that the surface of the ice-like matrix is microscopically flat and physically stable and can be applied as either a conductive or an insulting substrate for SECM studies. Perchlorate ion was selected as the common ion in both phases, the concentrations of which controlled the interfacial potential difference. The effect of perchlorate concentration in the DCE phase on interfacial reactions has been studied in detail. The apparent heterogeneous rate constants for TCNQ(.-) oxidation by Fe(CN)(6)(3-) in another phase under different temperatures have been calculated by a best-fit analysis, where the experimental approach curves are compared with the theoretically derived relationships. Reaction rate data obey Butler-Volmer formulation before and after the freezing point, which is similar to most other known cases of ET reactions at liquid/liquid interfaces. However, there is a sharp change observed for heterogeneous rate constants around the freezing point of the aqueous phase, which reflects the phase transition. At temperatures below -20 degreesC, surface-confined voltammograms for the reduction of ferricyanide were obtained, and the ice-like matrix became an insulating one, which indicates that the aqueous phase is really a frozen phase.

PROCESS OF PHOTOLUMINESCENCE AND PHOTOSTIMULATED LUMINESCENCE IN BAFBR-EU PHOSPHORS

The photoluminescence (PL) and photostimulated luminescence (PSL) of BaFBr: Eu phosphors are reported. In the photoluminescence of BaFBr:Eu, the emission of Eu2+, e-h recombination and Eu3+ have been observed, while in the photostimulated luminescence only the emission of Eu2+ was observed. This phenomenon may be explained well by the suggestion of a two-hand model for the host emission in which the host emission energy may transfer to Eu2+ difference of excitation in those two processes results in different transfer rates which makes the PL and PSL emission different.

Separation of Ce(IV) and RE(III) with hollow fiber membrane-based extraction

Separation of Ce(IV) and RE(III) was investigated by hollow fiber membrane-based extraction with contercurrent recirculating operation. The mass transfer coefficients of Ce(IV) and RE(III) and the effective factors to them were tested. The results show the mass transfer coefficient of Ce(IV) is larger than that of RE(III), and their mass transfer mechanism is different. The mass transfer of Ce(IV) was controlled by the resistance in water critical layer due to its more rapid interfacial reaction rate and larger distribution coefficient, which was different from RE(III) mass transfer with a slow interfacial reaction rate and small distribution coefficient. Ce(IV) was separated from the mixed solution of Ce(IV) and RE(III) by means of the difference of their mass transfer rates.

Electrochemical study of the interfacial characteristics of redox-active viologen thiol self-assembled monolayers

The electrochemical behavior of the electroactive self-assembled monolayers (SAMs) of thiol-functionalized viologen, CH3(CH2)(9)V2+(CH2)(8)SH, where V2+ is a viologen group, on the gold electrodes is examined by cyclic voltammetry and electrochemical a.c. impedance. A monolayer of viologen is immobilized on the gold electrode surface via the Au-S bond and the normal potentials corresponding to the two successive one-electron transfer processes of the viologen active centers are -310 mV and -652 mV (vs. Ag/AgCl) in 0.1 mol l(-1) phosphate buffer solution (pH 6.96) respectively. These results suggest that the viologen SAMs are stable and well-behaved monolayers. The experimental impedance data corresponding to different forms of viologen group have been fitted to equivalent electrical circuits, and the surface capacitances and resistances have been given. The heterogenous electron transfer rates of the first and the second redox processes are 7.57 s(-1) and 1.49 s(-1) respectively through a.c. impedance.

Effect of interfacial heat transfer on the onset of oscillatory convection in liquid bridge

In present study, effect of interfacial heat transfer with ambient gas on the onset of oscillatory convection in a liquid bridge of large Prandtl number on the ground is systematically investigated by the method of linear stability analyses. With both the constant and linear ambient air temperature distributions, the numerical results show that the interfacial heat transfer modifies the free-surface temperature distribution directly and then induces a steeper temperature gradient on the middle part of the free surface, which may destabilize the convection. On the other hand, the interfacial heat transfer restrains the temperature disturbances on the free surface, which may stabilize the convection. The two coupling effects result in a complex dependence of the stability property on the Biot number. Effects of melt free-surface deformation on the critical conditions of the oscillatory convection were also investigated. Moreover, to better understand the mechanism of the instabilities, rates of kinetic energy change and "thermal" energy change of the critical disturbances were investigated (C) 2009 Elsevier Ltd. All rights reserved.

Modelling Study On The Plasma Flow and Heat Transfer In A Laminar Arc Plasma Torch Operating At Atmospheric and Reduced Pressure

A modelling study is performed to investigate the characteristics of both plasma flow and heat transfer of a laminar non-transferred arc argon plasma torch operated at atmospheric and reduced pressure. It is found that the calculated flow fields and temperature distributions are quite similar for both cases at a chamber pressure of 1.0 atm and 0.1 atm. A fully developed flow regime could be achieved in the arc constrictor-tube between the cathode and the anode of the plasma torch at 1.0 atm for all the flow rates covered in this study. However the flow field could not reach the fully developed regime at 0.1 atm with a higher flow rate. The arc-root is always attached to the torch anode surface near the upstream end of the anode, i.e. the abruptly expanded part of the torch channel, which is in consistence with experimental observation. The surrounding gas would be entrained from the torch exit into the torch interior due to a comparatively large inner diameter of the anode channel compared to that of the arc constrictor-tube.