Theoretical prediction of the contact distance dependence of the electron transfer reactivity of the ClO/ClO− coupling system

On the basis of the structures and properties of the ClO/ClO^? system obtained at the density functional theory (DFT) (UB3LYP) level, employing the 6‐311+G(3df) standard basis set, the electron transfer reactivity of this system is investigated. The results indicate that there are five possible stable coupling complexes that correspond to the generous minima on the global potential energy surfaces (PES). The most stable coupling complex is planar EC4, in which there is a O? O linkage with two trans‐Cl atoms. Their stabilization energies are calculated to be 20.57 (EC1: C₁), 20.54 (EC2: C₂, ²B), 20.69 (EC3: C₁), 20.70 (EC4: C_s, ²A′), and 20.69 (EC.5: C_2h, ²B_u) kcal/mol at the B3LYP/6‐311+G(3df) level; with the correction of the basis set superposition error (BSSE), the stability order of these encounter complexes is EC4 > EC.5 > EC3 > EC1 > EC2. Based on the five encounter complexes, five coupling modes are designed for the study of the electron transfer reactivity of this system. The dissociation energy curves at the activated states and the corresponding activation energies of these five coupling modes are obtained and are compared at the B3LYP/6‐311+G(3df) and MP2/6‐311+G* levels. The inapplicability of DFT methods has also been discussed in this article in predicting the energy curves, especially with a long contact distance, in which DFT methods give the abnormal behavior for the dissociations of the complexes caused by the “inverse symmetry breaking” problem. On the basis of the golden rule of the time‐dependent perturbation theory, the electron transfer reactivity and the contact distance dependence of the various electron transfer kinetics parameters (e.g., activation energy, coupling matrix element) have been analyzed at the UMP2(full)/6‐311+G* level. The electron transfer can take place over a range of contact distances, but the most effective coupling distance corresponds to only a small range. The coupling orientation analyses also indicate that the most favorable coupling mode to the electron transfer does not always correspond to the most stable encounter complex mechanism. Some highly energetic coupling modes are more favorable for the electron transfer. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Electron impact ionization of Zn+ and Ga+

We have investigated the contribution of excitation-autoionization to the electron impact ionization of Zn⁺ and Ga⁺ using the binary encounter approximation. Hartree-Fock velocity distributions for the bound electrons have been used throughout the calculations of direct and indirect ionization cross-sections. The calculated cross-sections are in good agreement with recent experiments. We have also compared our results with other theoretical calculations.     

54Xe^q＋（q=1,2）与H和He碰撞的电荷剥离截面

采用二体碰撞近似和托马斯－费米近似方法计算了多电荷离子５４Ｘｅｑ＋ （ｑ ＝ １,２ ）与中性原子Ｈ和Ｈｅ 碰撞的电荷剥离截面、电子动量分布和离子势函数分布。计算结果与平面波玻恩近似结果符合得较好     

Electron impact single ionization of copper

Electron impact single ionization cross sections of copper have been calculated in the binary encounter approximation using accurate expression for σ _ΔE as given by Vriens and Hartree-Fock momentum distribution for the target electron. The BEA calculation based on the usual procedure does not show satisfactory agreement with experiment in this case but a striking modification is found to be successful in explaining the experimental observations. The discrepancy is linked with the ionization of the 3d ¹⁰ electrons and probably effective single ionization does not take place from 3d shell of copper leading to smaller values of experimental cross sections.     

Electron transfer reactivity of O2+O system in low-spin coupling: Ab Initio study at electron correlation level

The electron transfer reactivity of the O₂+O system in low-spin coupling is studied at the second-order unrestricted Møller–Plesset (full)/6-311+G* basis set level by using different transition state structures. The properties and stabilities of the encounter complexes are compared for the five selected coupling structures: two T type, collinear, parallel, and crossing. The activation barriers and the coupling matrix elements are also calculated. The results indicate that the structures of the encounter complexes directly affect the electron transfer mechanism and rate. These encounter complexes are structurally unstable, the contact distances between the acceptor O₂ and the donor O are generally large, the interaction is weak, and the structures are floppy. The electronic transmission factor for the reacting system, O₂+O, is less than unity; thus, the electron transfer reaction is nonadiabatic in nature. Analysis of the dependence of relevant kinetic parameters on various influencing factors has shown that the effect of the solvent medium on the coupling matrix element is small but that on the electron transfer rate is very large. Among the five selected transition state structures, the electron transfer is more likely to take place via T₁-type and P-type structures. In the low-spin coupling the favorable electronic states for two reacting species are ¹∑(O₂) and X²Π_g(O) instead of X³∑(O₂) and X²π_g(O), which are favorable for the high-spin (quartet state) coupling mechanism. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 989–998, 1999     

Random walk of annihilating particles on the ring

We obtain the formula for the transition probability of an arbitrary number of annihilating particles wandering along a ring-shaped one-dimensional lattice from the initial coordinates to the final coordinates during an arbitrary number of discrete time steps. __________ Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 146, No. 3, pp. 488–498, March, 2006.     

Efficient Encounter Complex Formation and Electron Transfer to Cytochrome c Peroxidase with an Additional,Distant Electrostatic Binding Site

Electrostatic interactions can strongly increase the efficiency of protein complex formation. The charge distribution in redox proteins is often optimized to steer a redox partner to the electron transfer active binding site. To test whether the optimized distribution is more important than the strength of the electrostatic interactions, an additional negative patch was introduced on the surface of cytochrome c peroxidase, away from the stereospecific binding site, and its effect on the encounter complex as well as the rate of complex formation was determined. Monte Carlo simulations and paramagnetic relaxation enhancement NMR experiments indicate that the partner, cytochrome c, interacts with the new patch. Unexpectedly, the rate of the active complex formation was not reduced, but rather slightly increased. The findings support the idea that for efficient protein complex formation the strength of the electrostatic interaction is more critical than an optimized charge distribution.     

On the Coherent Description of Diffusion‐Influenced Fluorescence Quenching Experiments II: Early Events

In a previous article we showed how to perform and analyze steady‐state and nanosecond time‐resolved experiments on fluorescence quenching by electron transfer in a coherent manner. Now, by making use of a superior time resolution, we explore the first stages of this kind of reaction. The novel information gained enables us to merge the results on the viscosity and the driving‐force dependencies of the reaction rate. A unique set of parameters for a single reaction channel suffices to describe all the results in the frame of differential encounter theory for diffusion‐influenced, bimolecular, remote electron‐transfer reactions. The inclusion of the solvent structure is crucial for the understanding of the reaction kinetics. To the authors’ best knowledge, this is the first time that such a comprehensive set of data has been successfully and jointly explained in the field, with physically sound parameters for electron‐transfer reactions.     

10Neq+(q=1～3)的电荷损失截面

采用托马斯－费米近似和二体碰撞近似,计算了多电荷离子１０Ｎｅ＾ｑ＋与中性原子Ｈ和Ｈｅ碰撞的电荷损失截面以及电子的动量分布和离子势函数分布。     

受周期外界环境影响的VanderPol情绪模型

本文以VanderPol方程为基础，建立了受周期外界环境刺激影响的非线性动态情绪模型，并在Matlab环境下实现了具有混沌性质的数值模拟，所建立的模型很好的模拟了情绪变化的规律，并为计算机实现智能化打下了基础。