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Issue 15, 2019
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Theory and practice of modeling van der Waals interactions in electronic-structure calculations

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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.

Graphical abstract: Theory and practice of modeling van der Waals interactions in electronic-structure calculations

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Publication details

The article was received on 21 Feb 2019 and first published on 13 Jun 2019


Article type: Review Article
DOI: 10.1039/C9CS00060G
Chem. Soc. Rev., 2019,48, 4118-4154

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    Theory and practice of modeling van der Waals interactions in electronic-structure calculations

    M. Stöhr, T. Van Voorhis and A. Tkatchenko, Chem. Soc. Rev., 2019, 48, 4118
    DOI: 10.1039/C9CS00060G

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