Granatier Jaroslav, Lazar Petr, Otyepka Michal, Hobza Pavel
J Chem Theory Comput. 2011 Nov 8;7(11):3743-3755. doi: 10.1021/ct200625h. Epub 2011 Oct 5.
The adsorption of Ag, Au, and Pd atoms on benzene, coronene, and graphene has been studied using post Hartree-Fock wave function theory (CCSD(T), MP2) and density functional theory (M06-2X, DFT-D3, PBE, vdW-DF) methods. The CCSD(T) benchmark binding energies for benzene-M (M = Pd, Au, Ag) complexes are 19.7, 4.2, and 2.3 kcal/mol, respectively. We found that the nature of binding of the three metals is different: While silver binds predominantly through dispersion interactions, the binding of palladium has a covalent character, and the binding of gold involves a subtle combination of charge transfer and dispersion interactions as well as relativistic effects. We demonstrate that the CCSD(T) benchmark binding energies for benzene-M complexes can be reproduced in plane-wave density functional theory calculations by including a fraction of the exact exchange and a nonempirical van der Waals correction (EE+vdW). Applying the EE+vdW method, we obtained binding energies for the graphene-M (M = Pd, Au, Ag) complexes of 17.4, 5.6, and 4.3 kcal/mol, respectively. The trends in binding energies found for the benzene-M complexes correspond to those in coronene and graphene complexes. DFT methods that use empirical corrections to account for the effects of vdW interactions significantly overestimate binding energies in some of the studied systems.
利用后哈特里-福克波函数理论（CCSD(T)、MP2）和密度泛函理论（M06-2X、DFT-D3、PBE、vdW-DF）方法，研究了银、金和钯原子在苯、并五苯和石墨烯上的吸附情况。苯-M（M = Pd、Au、Ag）配合物的CCSD(T)基准结合能分别为19.7、4.2和2.3千卡/摩尔。我们发现这三种金属的结合性质不同：银主要通过色散相互作用结合，钯的结合具有共价性质，而金的结合涉及电荷转移、色散相互作用以及相对论效应的微妙组合。我们证明，通过包含一部分精确交换和非经验范德华校正（EE+vdW），平面波密度泛函理论计算可以重现苯-M配合物的CCSD(T)基准结合能。应用EE+vdW方法，我们分别得到了石墨烯-M（M = Pd、Au、Ag）配合物的结合能为17.4、5.6和4.3千卡/摩尔。苯-M配合物的结合能趋势与并五苯和石墨烯配合物中的趋势一致。使用经验校正来考虑范德华相互作用影响的密度泛函理论方法在一些研究体系中显著高估了结合能。
