Theory and practice of modeling van der Waals interactions in electronic-structure calculations. (13th June 2019)

• Record Type: Journal Article
• Authors: Stöhr, Martin; Van Voorhis, Troy; Tkatchenko, Alexandre
• Is Part Of: Chemical Society reviews. Volume 48:Number 15(2019)
• Page Start: 4118
• Page End: 4154
• Publication Date: 2019-06-13
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/c9cs00060g
• Languages: English
• ISSNs: 0306-0012

Abstract

Abstract : Opening the black box of van der Waals-inclusive electronic structure calculations: a tutorial-style introduction to van der Waals dispersion interactions, state-of-the-art methods in computational modeling and complementary experimental techniques. Abstract : The accurate description of long-range electron correlation, most prominently including van der Waals (vdW) dispersion interactions, represents a particularly challenging task in the modeling of molecules and materials. vdW forces arise from the interaction of quantum-mechanical fluctuations in the electronic charge density. Within (semi-)local density functional approximations or Hartree–Fock theory such interactions are neglected altogether. Non-covalent vdW interactions, however, are ubiquitous in nature and play a key role for the understanding and accurate description of the stability, dynamics, structure, and response properties in a plethora of systems. During the last decade, many promising methods have been developed for modeling vdW interactions in electronic-structure calculations. These methods include vdW-inclusive Density Functional Theory and correlated post-Hartree–Fock approaches. Here, we focus on the methods within the framework of Density Functional Theory, including non-local van der Waals density functionals, interatomic dispersion models within many-body and pairwise formulation, and random phase approximation-based approaches. This review aims to guide the reader through the theoretical foundations of these methods in a tutorial-style manner and, in particular, highlight practical aspects such as the applicability and the advantages and shortcomings of current vdW-inclusive approaches. In addition, we give an overview of complementary experimental approaches, and discuss tools for the qualitative understanding of non-covalent interactions as well as energy decomposition techniques. Besides representing a reference for the current state-of-the-art, this work is thus also designed as a concise and detailed introduction to vdW-inclusive electronic structure calculations for a general and broad audience.