A computationally inexpensive modification of the point dipole electrostatic polarization model for molecular simulations
A computationally inexpensive modification of the point dipole electrostatic polarization model for molecular simulations
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DOI：
10.1002/jcc.10170
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发表时间：
2003-02-01
影响因子：
3
通讯作者：
Zhou, RH
中科院分区：
文献类型：
--
作者：
Kaminski, GA;Friesner, RA;Zhou, RH
我们提出了一个近似，它允许减少所需的计算资源，明确将静电极化到分子模拟利用经验力场。所提出的方法是用来计算三体能量的分子复合物与偶极静电探针，气相二聚能量，和纯液体性质的五个系统，是重要的生物物理和有机模拟水，甲醇，甲胺，甲硫醇，乙酰胺。在所有的情况下，三体能量符合高水平的从头算数据在0.07千卡/摩尔，二聚化能量-在0.43千卡/摩尔（除了特殊情况下的CH_3SH），和计算的汽化热和密度与实验结果相差小于2%。此外，由于所提出的方法可以显着降低计算成本，我们能够进行的液态计算与蒙特卡罗技术。与全尺寸点偶极子方法的比较表明，计算时间减少了3.5至20倍以上，这取决于手头的系统和全尺寸模型精度的期望水平，而在大多数情况下，全尺寸和近似模型之间的能量结果的差异并不大。与nonpolarizable OPLS-AA力场的所有涉及的物质和与极化的POL 3和Q90模型的水和甲醇，分别比较，表明所提出的技术可以降低计算成本，而不牺牲精度。我们希望所提出的方法将有助于分子模拟技术在生物物理和物理有机化学领域的研究。(C)2003 Wiley Periodicals，Inc.
We present an approximation, which allows reduction of computational resources needed to explicitly incorporate electrostatic polarization into molecular simulations utilizing empirical force fields. The proposed method is employed to compute three-body energies of molecular complexes with dipolar electrostatic probes, gas-phase dimerization energies, and pure liquid properties for five systems that are important in biophysical and organic simulations-water, methanol, methylamine, methanethiol, and acetamide. In all the cases, the three-body energies agreed with high level ab initio data within 0.07 kcal/mol, dimerization energies-within 0.43 kcal/mol (except for the special case of the CH3SH), and computed heats of vaporization and densities differed from the experimental results by less than 2%. Moreover, because the presented method allows a significant reduction in computational cost, we were able to carry out the liquid-state calculations with Monte Carlo technique. Comparison with the full-scale point dipole method showed that the computational time was reduced by 3.5 to more than 20 times, depending on the system in hand and on the desired level of the full-scale model accuracy, while the difference in energetic results between the full-scale and the presented approximate model was not great in the most cases. Comparison with the nonpolarizable OPLS-AA force field for all the substances involved and with the polarizable POL3 and q90 models for water and methanol, respectively, demonstrates that the presented technique allows reduction of computational cost with no sacrifice of accuracy. We hope that the proposed method will be of benefit to research employing molecular modeling technique in the biophysical and physical organic chemistry areas. (C) 2003 Wiley Periodicals, Inc.