A transferable polarizable electrostatic force field for molecular mechanics based on the chemical potential equalization principle
A transferable polarizable electrostatic force field for molecular mechanics based on the chemical potential equalization principle
复制标题
DOI：
10.1063/1.1515773
复制
发表时间：
2002-11-22
影响因子：
4.4
通讯作者：
Procacci, P
中科院分区：
文献类型：
--
作者：
Chelli, R;Procacci, P
提出了经典分子力学的极化静电势模型。该模型基于化学势均衡（CPE）原理，从Mortier， Ghosh， and Shankar的原始公式开始发展[J]。点。化学。社会科学。108,4315(1986)]。继York和Yang之后[J]。化学。[物理学报，104,159(1996)]我们提出了一种基于sp的CPE参数化来实际描述任何类型的分子系统。通过从头开始拟合电子性质，如偶极矩、极化率和有限有机分子的整体分子硬度，我们推导出原子参数，应用于更广泛的目标化合物集。我们确实表明，为分子的学习集计算的原子CPE参数为不包括在学习集中的各种化合物的几种电子性质提供了可靠的值。用CPE参数化得到的多极矩与常用的经典分子力学力场（如AMBER）的固定电荷参数化结果进行了比较。我们发现固定电荷参数化只能很好地再现用于拟合的分子构象或同分异构体的多极矩，而当考虑不同的分子构象或同分异构体时则不准确。相反，CPE模型真实地再现了分子核结构变化引起的电荷重组，如异构化或构象转变。CPE模型还在各种分子复合物上进行了测试，以研究实际分子-分子相互作用情况下的极化响应。本文的主要结果是证明了经典分子力学中一般极化静电力场的构造现在是一种可行的方法。(C) 2002年美国物理研究所。
A polarizable electrostatic potential model for classical molecular mechanics is presented. Based on the chemical potential equalization (CPE) principle, the model is developed starting from the original formulation of Mortier, Ghosh, and Shankar [J. Am. Chem. Soc. 108, 4315 (1986)]. Following York and Yang [J. Chem. Phys. 104, 159 (1996)] we present an SP-basis CPE parametrization to describe realistically any sort of molecular system. By fitting ab initio electronic properties, such as dipole moment, polarizability and global molecular hardness of a restricted set of organic molecules, we derive atomic parameters to be applied to a more vast target set of compounds. We show, indeed, that the atomic CPE parameters calculated for the learning set of molecules give reliable values for several electronic properties of various compounds not included in the learning set. The multipole moments obtained by using the proposed CPE parametrization are compared to the results of a fixed charge parametrization like that used by a popular classical molecular mechanics force field, such as AMBER. We show that the fixed charge parametrization can well reproduce only the multipole moments of the molecular conformation or the isomer used for the fit, while being inaccurate when different molecular conformations or isomers are considered. On the contrary, the CPE model realistically reproduces the charge reorganization due to nuclear structural changes of the molecule, such as isomerization or conformational transition. The CPE model has been also tested on various molecular complexes to investigate the polarization response in the case of realistic molecule-molecule interactions. The main result of the paper is the demonstration that the construction of a general polarizable electrostatic force field for classical molecular mechanics is now a viable way. (C) 2002 American Institute of Physics.