A new method to locate saddle points for reactions in solution by using the free-energy gradient method and the mean field approximation
A new method to locate saddle points for reactions in solution by using the free-energy gradient method and the mean field approximation
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DOI：
10.1002/jcc.20048
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发表时间：
2004-07-30
影响因子：
3
通讯作者：
Aguilar, MA
中科院分区：
文献类型：
--
作者：
Galván, IF;Martín, ME;Aguilar, MA
提出了一种计算溶液中反应鞍点的新方法。该方法的主要特点是：（1）溶质 - 溶剂体系由平均溶剂静电势/分子动力学方法（ASEP/MD）描述。这是一种量子力学/分子力学方法（QM/MM），它利用平均场近似（MFA），能够同时优化溶质分子的电子结构和几何结构以及其周围的溶剂结构。（2）通过联合使用自由能梯度法和平均场近似来确定过渡态。讨论了该方法在水溶液中氨（NH₃）和氯甲烷（CH₃Cl）之间的门秀金反应研究中的应用。通过与其他方法比较，检验了所提出方法的准确性和实用性。（C）2004威利期刊公司
A new method for calculating saddle points of reactions in Solution is presented. The main characteristics of the method are: (1) the solute-solvent system is described by the averaged solvent electrostatic potential/molecular dynamics method (ASEP/MD). This is a quantum mechanics/molecular mechanics method (QM/MM) that makes use of the mean field approximation (NIFA) and that permits one to simultaneously optimize the electronic structure and geometry of the Solute molecule and the solvent structure around it. (2) The transition state is located by the joint use of the free-energy gradient method and the mean field approximation. An application to the study of the Menshutkin reaction between NH3 and CH3Cl in aqueous solution is discussed. The accuracy and usefulness of the proposed method is checked through comparison with other methods. (C) 2004 Wiley Periodicals, Inc.