Institut für Physikalische Chemie und Elektrochemie, TU Dresden, D-01062 Dresden, Germany, Steacie Institute for Molecular Sciences, NRC, 100 Sussex Dr., Ottawa, Ontario K1A 0R6, Canada, and Departamento de Química-ICEx, Universidade Federal de Minas Gerais, 31270-901 Belo Horizonte, Brazil.
J Chem Theory Comput. 2005 Sep;1(5):841-7. doi: 10.1021/ct050065y.
The performance of density functional theory (DFT) (VWN-LDA, PBE-GGA, and B3LYP hybrid functionals), density-functional-based tight binding (DFTB), and ab initio methods [HF, MP2, CCSD, and CCSD(T)] for the treatment of London dispersion is investigated. Although highly correlated ab initio methods are capable of describing this phenomenon, if they are used with rather large basis sets, DFT methods are found to be inadequate for the description of H2/PAH (polycyclic aromatic hydrocarbon) interactions. As an alternative approach, an a posteriori addition of a van der Waals term to DFTB is proposed. This method provides results for H2/PAH interactions in close agreement with MP2 and higher-level ab initio methods. Bulk properties of graphite also compare well with the experimental data.
研究了密度泛函理论（DFT）（VWN-LDA、PBE-GGA 和 B3LYP 杂化泛函）、基于密度泛函的紧束缚（DFTB）和从头算方法[HF、MP2、CCSD 和 CCSD(T)]对伦敦色散的处理。尽管高度相关的从头算方法能够描述这种现象，但如果使用较大的基组，则发现 DFT 方法不足以描述 H2/PAH（多环芳烃）相互作用。作为一种替代方法，提出了向 DFTB 添加范德华项的后验方法。该方法提供的 H2/PAH 相互作用的结果与 MP2 和更高水平的从头算方法非常吻合。石墨的体性质也与实验数据很好地吻合。
