The Thomas Young Centre for Theory and Simulation of Materials, Imperial College London, London SW7 2AZ, United Kingdom.
J Chem Phys. 2011 Oct 21;135(15):154105. doi: 10.1063/1.3647912.
We investigate a recently developed approach [P. L. Silvestrelli, Phys. Rev. Lett. 100, 053002 (2008); J. Phys. Chem. A 113, 5224 (2009)] that uses maximally localized Wannier functions to evaluate the van der Waals contribution to the total energy of a system calculated with density-functional theory. We test it on a set of atomic and molecular dimers of increasing complexity (argon, methane, ethene, benzene, phthalocyanine, and copper phthalocyanine) and demonstrate that the method, as originally proposed, has a number of shortcomings that hamper its predictive power. In order to overcome these problems, we have developed and implemented a number of improvements to the method and show that these modifications give rise to calculated binding energies and equilibrium geometries that are in closer agreement to results of quantum-chemical coupled-cluster calculations.
我们研究了一种最近开发的方法[P. L. Silvestrelli, Phys. Rev. Lett. 100, 053002 (2008); J. Phys. Chem. A 113, 5224 (2009)]，该方法使用最大局域化 Wanier 函数来评估密度泛函理论计算的系统总能量中的范德华贡献。我们在一组原子和分子二聚体（氩、甲烷、乙烯、苯、酞菁和铜酞菁）上对其进行了测试，并证明该方法在最初提出时存在一些缺陷，这些缺陷阻碍了其预测能力。为了克服这些问题，我们对该方法进行了一些改进，并表明这些改进导致的计算结合能和平衡几何形状与量子化学耦合簇计算的结果更为一致。
