Paton Robert S, Goodman Jonathan M
Department of Chemistry, Unilever Centre for Molecular Science Informatics, Lensfield Road, Cambridge CB2 1EW, U.K.
J Chem Inf Model. 2009 Apr;49(4):944-55. doi: 10.1021/ci900009f.
We have evaluated the performance of a set of widely used force fields by calculating the geometries and stabilization energies for a large collection of intermolecular complexes. These complexes are representative of a range of chemical and biological systems for which hydrogen bonding, electrostatic, and van der Waals interactions play important roles. Benchmark energies are taken from the high-level ab initio values in the JSCH-2005 and S22 data sets. All of the force fields underestimate stabilization resulting from hydrogen bonding, but the energetics of electrostatic and van der Waals interactions are described more accurately. OPLSAA gave a mean unsigned error of 2 kcal mol(-1) for all 165 complexes studied, and outperforms DFT calculations employing very large basis sets for the S22 complexes. The magnitude of hydrogen bonding interactions are severely underestimated by all of the force fields tested, which contributes significantly to the overall mean error; if complexes which are predominantly bound by hydrogen bonding interactions are discounted, the mean unsigned error of OPLSAA is reduced to 1 kcal mol(-1). For added clarity, web-based interactive displays of the results have been developed which allow comparisons of force field and ab initio geometries to be performed and the structures viewed and rotated in three dimensions.
我们通过计算大量分子间复合物的几何结构和稳定化能，评估了一组广泛使用的力场的性能。这些复合物代表了一系列化学和生物系统，其中氢键、静电和范德华相互作用起着重要作用。基准能量取自JSCH - 2005和S22数据集中的高水平从头算值。所有力场都低估了氢键导致的稳定化作用，但静电和范德华相互作用的能量学描述得更准确。对于所研究的全部165种复合物，OPLSAA的平均绝对误差为2 kcal mol⁻¹，并且在S22复合物方面优于采用非常大基组的密度泛函理论（DFT）计算。所有测试的力场都严重低估了氢键相互作用的强度，这对整体平均误差有显著贡献；如果不考虑主要由氢键相互作用结合的复合物，OPLSAA的平均绝对误差会降至1 kcal mol⁻¹。为了更清晰地展示结果，已开发基于网络的交互式显示，可对力场和从头算几何结构进行比较，并能在三维空间中查看和旋转结构。
