Wong Bryan M
Materials Chemistry Department, Sandia National Laboratories, Livermore, California 94551, USA.
J Comput Chem. 2009 Jan 15;30(1):51-6. doi: 10.1002/jcc.21022.
Stimulated by the recent observation of pi-pi interactions between C60 and corannulene subunits in a molecular tweezer arrangement (J Am Chem Soc 2007, 129, 3842), a density functional theory study was performed to analyze the electronic structure and properties of various noncovalent corannulene complexes. The theoretical approach is first applied to corannulene complexes with a series of benchmark molecules (CH4, NH3, and H2O) using several new-generation density functionals. The performance of nine density functionals, illustrated by computing binding energies of the corannulene complexes, demonstrates that Zhao and Truhlar's MPWB1K and M05-2X functionals provide energies similar to that obtained at the SCS-MP2 level. In contrast, most of the other popular density functionals fail to describe this noncovalent interaction or yield purely repulsive interactions. Further investigations with the M05-2X functional show that the binding energy of C60 with corannulene subunits in the relaxed molecular receptor clip geometry is -20.67 kcal/mol. The results of this calculation further support the experimental interpretation of pure pi-pi interactions between a convex fullerene and the concave surfaces of two corannulene subunits.
受近期在分子镊子结构中观察到的C60与碗烯亚基之间π-π相互作用（《美国化学会志》2007年，129卷，3842页）的启发，开展了一项密度泛函理论研究，以分析各种非共价碗烯配合物的电子结构和性质。首先使用几种新一代密度泛函将该理论方法应用于碗烯与一系列基准分子（CH4、NH3和H2O）形成的配合物。通过计算碗烯配合物的结合能来说明的九种密度泛函的性能表明，赵和特鲁哈勒的MPWB1K和M05-2X泛函给出的能量与在SCS-MP2水平获得的能量相似。相比之下，大多数其他常用的密度泛函无法描述这种非共价相互作用或产生纯粹的排斥相互作用。使用M05-2X泛函的进一步研究表明，在松弛的分子受体夹几何结构中，C60与碗烯亚基的结合能为-20.67 kcal/mol。该计算结果进一步支持了对凸面富勒烯与两个碗烯亚基凹面之间纯粹π-π相互作用的实验解释。
