Design and application of a multicoefficient correlation method for dispersion interactions.
Design and application of a multicoefficient correlation method for dispersion interactions.
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DOI：
10.1063/1.1630955
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发表时间：
2004-01
期刊：
影响因子：
--
通讯作者：
Timothy J. Giese;D. York
中科院分区：
文献类型：
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作者：
Timothy J. Giese;D. York
本文提出了一种新的确定精确货车范德华相互作用的多系数相关法（MCCM）。该方法利用了一种新的参数化策略，同时适合非常高的水平结合，Hartree-Fock和相关能量的同质和异质稀有气体二聚体的He，Ne和Ar。能量分解为Hartree-Fock和相关分量导致更可转移的模型。该方法适用于氪二聚体系统，稀有气体-水的相互作用，和三体相互作用的稀有气体三聚体He 3，Ne 3，和Ar 3。对于后者，一个非常高的水平的方法，修正的稀有气体两体相互作用的总结合能。与使用大基组的高水平CCSD（T）计算的比较表明，MCCM方法可转移到参数化中未考虑的各种系统。该方法允许较大系统的色散相互作用进行可靠的研究，在一小部分的计算成本，并提供了一个新的工具，应用到稀有气体集群，和分子模拟力场和新的半经验量子模型的色散参数的发展。
A new multicoefficient correlation method (MCCM) is presented for the determination of accurate van der Waals interactions. The method utilizes a novel parametrization strategy that simultaneously fits to very high-level binding, Hartree-Fock and correlation energies of homo- and heteronuclear rare gas dimers of He, Ne, and Ar. The decomposition of the energy into Hartree-Fock and correlation components leads to a more transferable model. The method is applied to the krypton dimer system, rare gas-water interactions, and three-body interactions of rare gas trimers He3, Ne3, and Ar3. For the latter, a very high-level method that corrects the rare-gas two-body interactions to the total binding energy is introduced. A comparison with high-level CCSD(T) calculations using large basis sets demonstrates the MCCM method is transferable to a variety of systems not considered in the parametrization. The method allows dispersion interactions of larger systems to be studied reliably at a fraction of the computational cost, and offers a new tool for applications to rare-gas clusters, and the development of dispersion parameters for molecular simulation force fields and new semiempirical quantum models.