Mulliken Center for Theoretical Chemistry, Universität Bonn , 53113 Bonn, Germany.
Chem Rev. 2016 May 11;116(9):5105-54. doi: 10.1021/acs.chemrev.5b00533. Epub 2016 Apr 14.
Mean-field electronic structure methods like Hartree-Fock, semilocal density functional approximations, or semiempirical molecular orbital (MO) theories do not account for long-range electron correlation (London dispersion interaction). Inclusion of these effects is mandatory for realistic calculations on large or condensed chemical systems and for various intramolecular phenomena (thermochemistry). This Review describes the recent developments (including some historical aspects) of dispersion corrections with an emphasis on methods that can be employed routinely with reasonable accuracy in large-scale applications. The most prominent correction schemes are classified into three groups: (i) nonlocal, density-based functionals, (ii) semiclassical C6-based, and (iii) one-electron effective potentials. The properties as well as pros and cons of these methods are critically discussed, and typical examples and benchmarks on molecular complexes and crystals are provided. Although there are some areas for further improvement (robustness, many-body and short-range effects), the situation regarding the overall accuracy is clear. Various approaches yield long-range dispersion energies with a typical relative error of 5%. For many chemical problems, this accuracy is higher compared to that of the underlying mean-field method (i.e., a typical semilocal (hybrid) functional like B3LYP).
平均场电子结构方法，如 Hartree-Fock、半局部密度泛函近似或半经验分子轨道 (MO) 理论，无法解释长程电子相关（伦敦色散相互作用）。对于大型或凝聚态化学系统的实际计算以及各种分子内现象（热化学），必须包含这些效应。本综述描述了色散校正的最新发展（包括一些历史方面），重点介绍了可在大规模应用中以合理精度常规使用的方法。最突出的校正方案分为三类：(i) 非局部、基于密度的泛函，(ii) 半经典 C6 基，和 (iii) 单电子有效势。这些方法的性质以及优缺点被批判性地讨论，并提供了分子配合物和晶体的典型实例和基准。尽管还有一些需要进一步改进的领域（稳健性、多体和短程效应），但关于整体准确性的情况很清楚。各种方法都能以典型的相对误差 5% 产生长程色散能。对于许多化学问题，这种精度比基础平均场方法（即，B3LYP 等典型的半局部（混合）泛函）更高。
