PuO的基态分子结构与相对论有效原子实势

Three kinds of Relativistic Effective Core Potentials (RECP) with B3LYP, MP2 and HF methods have been used to work out the structures for the ground state of PuO molecule, whose equilibrium nuclear distances, disassociation energies, spectral constants and harmonic frequencies have been obtained. The ab initio energy data of PuO have been least-square-fitted to the Murrell-Sorbie potential energy function, from which the corresponding spectral constants, the second, third and forth forcec on stants have been derived. The results indicate that SDDRECP with B3LYP method could give the best calculations in agreement with the experimental results. The charge populations, spindensities and dipole moments of PuO molecule to the different RECP sand calculation levels have also been tabled out.     

New ab initio Potential Energy Surfaces for Cl（^2P3/2,^2P1/2）＋H2 Reaction

New global three dimensional potential energy surfaces for the Cl＋H2 reactive system have been constructed using accurate multireference configuration interaction calculations with a large basis set. The three lowest adiabatic potential energy surfaces correlating asymptotically with Cl（^2p）＋H2 have been transformed to adiabatic representation, which leads to a fourth coupling potential for non-linear geometries. In addition, the spin-orbit coupling surfaces have also been computed using the Breit-Pauli Hamiltonian. Properties of the new potential are described. Reaction dynamics based on the new potential agrees with the recent experimental results quite well.     

Evaluation of the proton transfer kinetics of potential electrolytes in non-aqueous solutions using electrochemical techniques Part 1. Kinetic analysis of the general CE mechanism at stationary and rotating electrodes

The transport and kinetics of potential electrolytes (such as weak organic acids) at stationary and rotating electrodes have been examined in detail. A coherent mathematical analysis enabling the normalised current response to be evaluated has been developed, and various rate limiting scenarios have been identified and examined. Received: 13 March 1998 / Accepted: 31 July 1998     

Regular Splitting and Potential Reduction Method for Solving Quadratic Programming Problem with Box Constraints

A regular splitting and potential reduction method is presented for solving a quadratic programming problem with box constraints (QPB) in this paper. A general algorithm is designed to solve the QPB problem and generate a sequence of iterative points. We show that the number of iterations to generate an e-minimum solution or an e-KKT solution by the algorithm is bounded by O( nlog(1 )), and the total running time is bounded by O(n2(n logn log1/ε)(n/εlog1/ε logn)) arithmetic operations.     

硝基甲烷异构化反应势能面的ab initio研究

在B3LYP/6-311+ +G(2d,2p)水平上,优化得到硝基甲烷CH3NO2的10种异构体和23个异构化反应过渡态,并用G2MP2方法进行了单点能计算.根据计算得到的G2MP2相对能量,探讨了CH3NO2势能面上异构化反应的微观机理.研究表明,反应初始阶段的CH3NO2异构化过程具有较高的能垒,其中CH3NO2的两个主要异构化反应通道,即CH3NO2→CH3ONO和CH3NO2→CH2N(O)OH的活化能分别为270.3和267.8 kJ/mol,均高于CH3NO2的C-N键离解能.因而,从动力学角度考虑, CH3NO2的异构化反应较为不利.     

隧道电子和局域场对固液界面纳米区域反应的影响——控电位下的Si(111)表面的STM诱导纳米刻蚀

隧道电子和局域场对固液界面纳米区域反应的影响①——控电位下的Ｓｉ（１１１）表面的ＳＴＭ诱导纳米刻蚀谢兆雄＊蔡雄伟施财辉毛秉伟田昭武（厦门大学固体表面物理化学国家重点实验室物理化学研究所化学系厦门３６１００５）扫描隧道显微技术（ＳＴＭ）目前已成为纳米加...     

广义协调技术与双参数法

本文对最近几年发展出的基于修正势能泛函的广义协调方法作一概述,并进一步介绍了作为这类方法更一般化的双参数有限元法      

3-羟基对氧萘酮分子内激发态质子转移反应位能面和机理的研究

用MNDO和INDO-SCF-CI法研究了3-羟基对氧萘酮分子内激发态质子转移反应基态和激发态的位能面,求得相应能垒△E₁、△E₂和荧光移位,并对光化学反应机理进行了探讨.     

Time-dependent Wave Packet Quantum Scattering Study of Reaction S(3P)+H2→HS+H on a New ab initio Potential Energy Surface 3A'

A new potential energy surface is presented for the triplet state ³A' of the chemical reaction S(³P)+H₂ from a set of accurate ab initio data. The single point energies are computed using highly correlated complete active space self-consistent-field and multi-reference config-uration interaction wave functions with a basis set of aug-cc-pV5Z. We have fitted the full set of energy values using many-body expansion method with an Aguado-Paniagua function. Based on the new potential energy surface, we carry out the time-dependent wave packet scattering calculations over the collision energy range of 0.8～2.2 eV. Both the centrifugal-sudden approximation and Coriolis Coupling cross sections are obtained. In addition, the total reaction probabilities are calculated for the reactant H₂ initially in the vibrational states v=0～3 (j=0). It is found that initial vibrational excitation enhances the title reaction.     

An ab initio potential energy surface and spectroscopic constants for the XΣg state of NO2

A three-dimensional potential energy function has been calculated for the X¹Σ⁺_g state of NO⁺₂ from ab initio MRD-CI data. With this PE function, converged vibrational calculations have also been performed for ten vibrational states, with the aid of a computer program developed in the present work for this purpose. The calculated harmonic frequencies, vibrational term values and rotational constants are in good agreement with experimental data.