Fritz-Haber-Institut der Max-Planck-Gesellschaft , Faradayweg 4-6, 14195 Berlin, Germany.
Department of Chemistry and Chemical Biology, Cornell University , Ithaca, New York 14853, United States.
Chem Rev. 2017 Mar 22;117(6):4714-4758. doi: 10.1021/acs.chemrev.6b00446. Epub 2017 Mar 8.
Noncovalent van der Waals (vdW) or dispersion forces are ubiquitous in nature and influence the structure, stability, dynamics, and function of molecules and materials throughout chemistry, biology, physics, and materials science. These forces are quantum mechanical in origin and arise from electrostatic interactions between fluctuations in the electronic charge density. Here, we explore the conceptual and mathematical ingredients required for an exact treatment of vdW interactions, and present a systematic and unified framework for classifying the current first-principles vdW methods based on the adiabatic-connection fluctuation-dissipation (ACFD) theorem (namely the Rutgers-Chalmers vdW-DF, Vydrov-Van Voorhis (VV), exchange-hole dipole moment (XDM), Tkatchenko-Scheffler (TS), many-body dispersion (MBD), and random-phase approximation (RPA) approaches). Particular attention is paid to the intriguing nature of many-body vdW interactions, whose fundamental relevance has recently been highlighted in several landmark experiments. The performance of these models in predicting binding energetics as well as structural, electronic, and thermodynamic properties is connected with the theoretical concepts and provides a numerical summary of the state-of-the-art in the field. We conclude with a roadmap of the conceptual, methodological, practical, and numerical challenges that remain in obtaining a universally applicable and truly predictive vdW method for realistic molecular systems and materials.
非共价范德华（vdW）或色散力在自然界中无处不在，影响着化学、生物学、物理学和材料科学中分子和材料的结构、稳定性、动力学和功能。这些力源于量子力学，源于电子电荷密度涨落之间的静电相互作用。在这里，我们探讨了精确处理 vdW 相互作用所需的概念和数学要素，并根据绝热连接涨落耗散（ACFD）定理（即 Rutgers-Chalmers vdW-DF、Vydrov-Van Voorhis（VV）、交换空穴偶极矩（XDM）、Tkatchenko-Scheffler（TS）、多体色散（MBD）和随机相位近似（RPA）方法），提出了一种系统而统一的分类当前第一性原理 vdW 方法的框架。特别关注多体 vdW 相互作用的有趣性质，其基本相关性最近在几项具有里程碑意义的实验中得到了强调。这些模型在预测结合能以及结构、电子和热力学性质方面的性能与理论概念相关联，并提供了该领域最新技术的数值总结。最后，我们提出了一个概念、方法、实践和数值方面的路线图，这些方面仍然存在获得适用于现实分子系统和材料的通用且真正可预测的 vdW 方法的挑战。
