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Title: First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

Abstract

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.

Authors:
 [1];  [2]; ORCiD logo [3]
  1. Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
  2. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States
  3. Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany; Physics and Materials Science Research Unit, University of Luxembourg, L-1511 Luxembourg, Luxembourg
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1480082
DOE Contract Number:  
AC02-06CH11357; AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Chemical Reviews
Additional Journal Information:
Journal Volume: 117; Journal Issue: 6; Journal ID: ISSN 0009-2665
Country of Publication:
United States
Language:
English

Citation Formats

Hermann, Jan, DiStasio, Robert A., and Tkatchenko, Alexandre. First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications. United States: N. p., 2017. Web. doi:10.1021/acs.chemrev.6b00446.
Hermann, Jan, DiStasio, Robert A., & Tkatchenko, Alexandre. First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications. United States. doi:10.1021/acs.chemrev.6b00446.
Hermann, Jan, DiStasio, Robert A., and Tkatchenko, Alexandre. Wed . "First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications". United States. doi:10.1021/acs.chemrev.6b00446.
@article{osti_1480082,
title = {First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications},
author = {Hermann, Jan and DiStasio, Robert A. and Tkatchenko, Alexandre},
abstractNote = {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.},
doi = {10.1021/acs.chemrev.6b00446},
journal = {Chemical Reviews},
issn = {0009-2665},
number = 6,
volume = 117,
place = {United States},
year = {2017},
month = {3}
}