McDaniel Jesse G, Schmidt J R
Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin-Madison , Madison, Wisconsin 53706, United States.
J Phys Chem B. 2014 Jul 17;118(28):8042-53. doi: 10.1021/jp501128w. Epub 2014 Apr 2.
We extend our previously developed approach for generating "physically-motivated" force fields from symmetry-adapted perturbation theory by introducing explicit terms to account for nonadditive three-body exchange and dispersion interactions, yielding transferability from the gas- to condensed-phase. These Axilrod-Teller-Muto-type three-body terms require no additional parametrization and can be implemented with high computational efficiency. We demonstrate the accuracy of our force fields for a diverse set of six organic liquids/fluids, examining a wide variety of structural, thermodynamic, and dynamic properties. We find that three-body dispersion and exchange interactions make significant contributions to the internal pressure of condensed phase systems and cannot be neglected in truly ab initio force field development. These resulting force field parameters are extremely transferable over wide ranges in temperature and pressures and across chemical systems, and should be widely applicable in condensed phase simulation.
我们扩展了之前开发的方法，通过引入明确的项来考虑非加性三体交换和色散相互作用，从对称适应微扰理论生成“具有物理动机”的力场，从而实现从气相到凝聚相的可转移性。这些Axilrod-Teller-Muto型三体项无需额外参数化，并且可以高效地实现。我们展示了我们的力场对于六种不同有机液体/流体的准确性，研究了各种各样的结构、热力学和动力学性质。我们发现三体色散和交换相互作用对凝聚相系统的内压有显著贡献，在真正的从头算力场开发中不能被忽略。这些得到的力场参数在温度和压力的广泛范围内以及跨化学系统都具有极高的可转移性，并且应该在凝聚相模拟中得到广泛应用。
