Fernandez Nicolas, Ferro Yves, Carissan Yannick, Marchois Julien, Allouche Alain
Aix-Marseille Université, CNRS, PIIM UMR 7345, 13 397 Marseille, France.
Phys Chem Chem Phys. 2014 Feb 7;16(5):1957-66. doi: 10.1039/c3cp54062f.
The interaction of beryllium with benzene, graphene and graphitic compounds involves multi-reference electronic states, Jahn-Teller distortion, charge transfer and van der Waals interactions. This is investigated herein using periodic and molecular models at different levels of theory: (i) the second-order Møller-Plesset (MP2) perturbation theory, (ii) the coupled cluster method with inclusion of single double and perturbative triple excitations (CCSD(T)), (iii) the complete active space self-consistent field (CAS-SCF) and (iv) the complete active space with perturbation theory truncated at the 2nd order (CAS-PT2). Molecular and periodic Density Functional Theory (DFT) methods are also used. The two major failures of DFT are addressed with regard to the beryllium benzene and graphene interaction: the degeneracy problem is the source of no specific problem while the delocalization error causes DFT with the Perdew Burke, Ernzerhof functional plus the Grimme correction (DFT/PBE-D2) to be over-binding by about 0.4 eV at a short-range. The agreement between DFT/PBE-D2 and wave-function based methods is nevertheless good; DFT/PBE-D2 provides an accurate description of the electronic structure of the system. By the end of this work, we shall get a better insight into the mechanisms leading beryllium to physisorb on graphene and to chemisorb into the bilayer of graphite.
铍与苯、石墨烯及石墨化合物的相互作用涉及多参考电子态、 Jahn-Teller 畸变、电荷转移和范德华相互作用。本文使用不同理论水平的周期性和分子模型对此进行了研究：(i) 二阶 Møller-Plesset (MP2) 微扰理论；(ii) 包含单双激发和微扰三激发的耦合簇方法 (CCSD(T))；(iii) 完全活性空间自洽场 (CAS-SCF)；以及 (iv) 二阶截断微扰理论的完全活性空间 (CAS-PT2)。还使用了分子和周期性密度泛函理论 (DFT) 方法。对于铍与苯及石墨烯的相互作用，讨论了 DFT 的两个主要缺陷：简并问题并非特定问题的根源，而定域误差导致采用 Perdew Burke Ernzerhof 泛函加上 Grimme 校正的 DFT (DFT/PBE-D2) 在短程时结合能高估约 0.4 eV。不过，DFT/PBE-D2 与基于波函数的方法之间的一致性良好；DFT/PBE-D2 对系统的电子结构提供了准确描述。在这项工作结束时，我们将对铍在石墨烯上物理吸附以及在石墨双层中化学吸附的机制有更深入的了解。
