物理化学学报2009，Vol.25Issue(7)：1439-1442,4.
一种确定反应中间态几何特征和能量的综合性方法
A Combined Method for Determining Reaction Transition State Geometry and Energy
摘要
Abstract
We found an alternative method for the derivation of transition state structure energy in chemical reactions which would be less dependent on the starting geometry of reactants by combining a mathematical tool and artificial neural networks(ANN)with conventional transition state optimization algorithms.When two reactants approach each other,every geometric structure corresponds to a system energy value.The purpose of this investigation was to collect as many energy values on the reaction energy surface as possible.By simulating the energy surface using the geometric parameters as independent variables,the first order saddle point in the energy surface corresponding to the transition state slyucture was derived.The nucleophilic attack step of a classical Aldol reaction was studied using acetaldehyde anion and formaldehyde as reactants.The intrinsic reaction coordinate(IRC)path calculation started with 3 different sets of starting reactant geometries and 96 points on the reaction energy surface were derived.The energy surface Was simulated using ANN.Cross-validation was applied to evaluate the result and avoided a possible overfilling of the ANN.关键词
反应过渡态/反应物几何构象/人工神经网络/反应势能面/一阶鞍点/交叉验证Key words
Reaction transition state/Geometry of reactant/Artificial neural network/Reaction energy surface/Firstorder saddle point/Cross-validation分类
化学化工引用本文复制引用
郑铮,刘振明,张亮仁..一种确定反应中间态几何特征和能量的综合性方法[J].物理化学学报,2009,25(7):1439-1442,4.基金项目
国家高技术研究发展计划(863)(2006AA02Z337)资助The project was supported by the National High-Tech Research and Development Program of China(863)(2006AA02Z337). （863）
