Accurate and Compatible Force Fields for Molecular Oxygen, Nitrogen, and Hydrogen to Simulate Gases, Electrolytes, and Heterogeneous Interfaces
Accurate and Compatible Force Fields for Molecular Oxygen, Nitrogen, and Hydrogen to Simulate Gases, Electrolytes, and Heterogeneous Interfaces
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准确且兼容的氧、氮和氢分子力场，可模拟气体、电解质和异质界面
DOI：
10.1021/acs.jctc.0c01132
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发表时间：
2021
影响因子：
5.5
通讯作者：
Heinz, Hendrik
中科院分区：
文献类型：
--
作者：
Wang, Shiyi;Hou, Kaiyi;Heinz, Hendrik
气体分子以及与液体和固体的界面在生物体、吸附、催化和环境中发挥着关键作用。在实验中监测吸附和异质界面仍然很困难，早期的分子模拟模型导致基本分子特性的误差超过 100%。我们在概念上引入了氧分子、氮分子和氢分子的新力场参数，将偏差减少到 <5%。我们将谐波键伸缩势和 Lennard-Jones 参数与 12-6 和 9-6 选项相结合，计算出的键长、拉曼峰、液体密度、汽化焓和水合自由能与实验非常一致。在验证密度和汽化能后获得了可靠的水合自由能，无需进行进一步的参数调整。我们举例说明了 Pt 电催化剂上的 O2 吸附和沸石中的 N2 吸附的应用，结果显示，在没有额外拟合参数的情况下，实验中测量的吸附能偏差 <5%。我们讨论所有参数的化学解释，并解释早期模型中差异的原因。与界面力场 (IFF)、CHARMM、AMBER、OPLS-AA、GROMOS、DREIDING、CVFF、PCFF、COMPASS 和 QM/MM 方法兼容，可以可靠地模拟气体以及液体/固体与生物聚合物、矿物和金属的界面。参数化协议可以应用于类似的分子。
Gas molecules and interfaces with liquids and solids play a critical role in living organisms, sorption, catalysis, and the environment. Monitoring adsorption and heterogeneous interfaces remains difficult in experiments, and earlier models for molecular simulations lead to errors over 100% in fundamental molecular properties. We introduce conceptually new force field parameters for molecular oxygen, nitrogen, and hydrogen that reduce deviations to <5%. We employ a combination of a harmonic bond stretching potential and Lennard-Jones parameters with 12-6 and 9-6 options, leading to computed bond lengths, Raman peaks, liquid densities, vaporization enthalpies, and free energies of hydration in impressive agreement with experiments. Reliable free energies of hydration were obtained upon validation of density and vaporization energy without significant further parameter adjustments. We illustrate applications to O2adsorption on Pt electrocatalysts and N2adsorption in zeolites, showing <5% deviation in adsorption energies measured in experiments without additional fitting parameters. We discuss the chemical interpretation of all parameters and explain the reasons for discrepancies in earlier models. Compatibility with the Interface Force Field (IFF), CHARMM, AMBER, OPLS-AA, GROMOS, DREIDING, CVFF, PCFF, COMPASS, and QM/MM methods enables reliable simulations of gases and liquid/solid interfaces with biopolymers, minerals, and metals. The parametrization protocol can be applied to similar molecules.