Steinmann Stephan N, Corminboeuf Clémence
Laboratory for Computational Molecular Design, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne.
Chimia (Aarau). 2011;65(4):240-4. doi: 10.2533/chimia.2011.240.
Density functional approximations fail to provide an accurate treatment of weak interactions. More recent, but not readily available functionals can lead to significant improvements. A simple alternative to correct for the missing weak interactions is to add, a posteriori, an atom pair-wise dispersion correction. We here present a density dependent dispersion correction, dDXDM, which dramatically improves the performance of popular functionals (e.g., PBE-dDXDM or B3LYP-dDXDM) for a set of 145 systems featuring both inter- and intramolecular interactions. Whereas the highly parameterized M06-2X functional, the long-range corrected LC-BLYP and the fully non-local van der Waals density functional rPW86-W09 also lead to improved results as compared to standard DFT methods, the enhanced performance of dDXDM remains the most impressive.
密度泛函近似无法对弱相互作用进行准确处理。更新的但不易获取的泛函可能会带来显著改进。一种校正缺失弱相互作用的简单替代方法是事后添加原子对间色散校正。我们在此提出一种密度依赖的色散校正方法dDXDM，对于一组包含分子间和分子内相互作用的145个体系，它能显著提高常用泛函（如PBE-dDXDM或B3LYP-dDXDM）的性能。与标准密度泛函理论（DFT）方法相比，虽然高度参数化的M06-2X泛函、长程校正的LC-BLYP以及完全非局部的范德华密度泛函rPW86-W09也能得到改进结果，但dDXDM的增强性能仍然最为显著。
