Linear scaling explicitly correlated MP2-F12 and ONIOM methods for the long-range interactions of the nanoscale clusters in methanol aqueous solutions.
Linear scaling explicitly correlated MP2-F12 and ONIOM methods for the long-range interactions of the nanoscale clusters in methanol aqueous solutions.
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DOI：
10.1063/1.4773011
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发表时间：
2013-01
期刊：
影响因子：
--
通讯作者：
Wei Li
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文献类型：
--
作者：
Wei Li
线性尺度量子化学方法，广义能量碎裂（GEBF）方法已扩展到显式相关的二阶Møller-Plesset微扰理论F12（MP2-F12）方法和自己的N层集成分子轨道分子力学（ONIOM）方法，其中GEBF-MP2-F12、GEBF-MP2和常规密度泛函方法 紧束缚方法可用于不同的层。然后，通过计算取自经典分子动力学（MD）快照的不同尺寸的气相和凝聚相甲醇-水簇中甲醇分子和水分子之间的结合能，研究稀甲醇水溶液中的长程相互作用。通过与SPC、TIP3P、PCFF和AMOEBA09等力场方法的结果进行比较，GEBF-MP2-F12和GEBF-ONIOM方法被证明对于研究高水平的长程相互作用是强大和高效的。利用GEBF-ONIOM(MP2-F12:MP2)和GEBF-ONIOM(MP2-F12:MP2:cDFTB)方法，所研究的最大纳米级团簇的直径分别约为2.4 nm（747个原子和10 209个具有aug-cc-pVDZ基组的基函数）和4 nm（3 351个原子），这几乎是不可能的 采用常规MP2或MP2-F12方法进行处理。因此，GEBF-F12和GEBF-ONIOM方法有望成为研究凝聚相纳米级团簇的实用工具，为从头计算和密度泛函理论研究提供替代基准，并与经典MD模拟相结合开发新的力场。
A linear scaling quantum chemistry method, generalized energy-based fragmentation (GEBF) approach has been extended to the explicitly correlated second-order Møller-Plesset perturbation theory F12 (MP2-F12) method and own N-layer integrated molecular orbital molecular mechanics (ONIOM) method, in which GEBF-MP2-F12, GEBF-MP2, and conventional density functional tight-binding methods could be used for different layers. Then the long-range interactions in dilute methanol aqueous solutions are studied by computing the binding energies between methanol molecule and water molecules in gas-phase and condensed phase methanol-water clusters with various sizes, which were taken from classic molecular dynamics (MD) snapshots. By comparing with the results of force field methods, including SPC, TIP3P, PCFF, and AMOEBA09, the GEBF-MP2-F12 and GEBF-ONIOM methods are shown to be powerful and efficient for studying the long-range interactions at a high level. With the GEBF-ONIOM(MP2-F12:MP2) and GEBF-ONIOM(MP2-F12:MP2:cDFTB) methods, the diameters of the largest nanoscale clusters under studies are about 2.4 nm (747 atoms and 10 209 basis functions with aug-cc-pVDZ basis set) and 4 nm (3351 atoms), respectively, which are almost impossible to be treated by conventional MP2 or MP2-F12 method. Thus, the GEBF-F12 and GEBF-ONIOM methods are expected to be a practical tool for studying the nanoscale clusters in condensed phase, providing an alternative benchmark for ab initio and density functional theory studies, and developing new force fields by combining with classic MD simulations.