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Title: How important is self-consistency for the dDsC density dependent dispersion correction?

Abstract

The treatment of dispersion interactions is ubiquitous but computationally demanding for seamless ab initio approaches. A highly popular and simple remedy consists in correcting for the missing interactions a posteriori by adding an attractive energy term summed over all atom pairs to standard density functional approximations. These corrections were originally based on atom pairwise parameters and, hence, had a strong touch of empiricism. To overcome such limitations, we recently proposed a robust system-dependent dispersion correction, dDsC, that is computed from the electron density and that provides a balanced description of both weak inter- and intramolecular interactions. From the theoretical point of view and for the sake of increasing reliability, we here verify if the self-consistent implementation of dDsC impacts ground-state properties such as interaction energies, electron density, dipole moments, geometries, and harmonic frequencies. In addition, we investigate the suitability of the a posteriori scheme for molecular dynamics simulations, for which the analysis of the energy conservation constitutes a challenging tests. Our study demonstrates that the post-SCF approach in an excellent approximation.

Authors:
;  [1];  [1]
  1. Laboratory for Computational Molecular Design, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne (Switzerland)
Publication Date:
OSTI Identifier:
22253484
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 140; Journal Issue: 18; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; APPROXIMATIONS; DENSITY; DENSITY FUNCTIONAL METHOD; DIPOLE MOMENTS; DISPERSIONS; ELECTRON DENSITY; ENERGY CONSERVATION; GROUND STATES; INTERACTIONS; MOLECULAR DYNAMICS METHOD; SIMULATION

Citation Formats

Brémond, Éric, Corminboeuf, Clémence, Golubev, Nikolay, Department of Chemistry, M. V. Lomonosov Moscow State University, Moscow 119991, Steinmann, Stephan N., E-mail: sns25@duke.edu, and Department of Chemistry, Duke University, Durham, North Carolina 27708. How important is self-consistency for the dDsC density dependent dispersion correction?. United States: N. p., 2014. Web. doi:10.1063/1.4867195.
Brémond, Éric, Corminboeuf, Clémence, Golubev, Nikolay, Department of Chemistry, M. V. Lomonosov Moscow State University, Moscow 119991, Steinmann, Stephan N., E-mail: sns25@duke.edu, & Department of Chemistry, Duke University, Durham, North Carolina 27708. How important is self-consistency for the dDsC density dependent dispersion correction?. United States. https://doi.org/10.1063/1.4867195
Brémond, Éric, Corminboeuf, Clémence, Golubev, Nikolay, Department of Chemistry, M. V. Lomonosov Moscow State University, Moscow 119991, Steinmann, Stephan N., E-mail: sns25@duke.edu, and Department of Chemistry, Duke University, Durham, North Carolina 27708. 2014. "How important is self-consistency for the dDsC density dependent dispersion correction?". United States. https://doi.org/10.1063/1.4867195.
@article{osti_22253484,
title = {How important is self-consistency for the dDsC density dependent dispersion correction?},
author = {Brémond, Éric and Corminboeuf, Clémence and Golubev, Nikolay and Department of Chemistry, M. V. Lomonosov Moscow State University, Moscow 119991 and Steinmann, Stephan N., E-mail: sns25@duke.edu and Department of Chemistry, Duke University, Durham, North Carolina 27708},
abstractNote = {The treatment of dispersion interactions is ubiquitous but computationally demanding for seamless ab initio approaches. A highly popular and simple remedy consists in correcting for the missing interactions a posteriori by adding an attractive energy term summed over all atom pairs to standard density functional approximations. These corrections were originally based on atom pairwise parameters and, hence, had a strong touch of empiricism. To overcome such limitations, we recently proposed a robust system-dependent dispersion correction, dDsC, that is computed from the electron density and that provides a balanced description of both weak inter- and intramolecular interactions. From the theoretical point of view and for the sake of increasing reliability, we here verify if the self-consistent implementation of dDsC impacts ground-state properties such as interaction energies, electron density, dipole moments, geometries, and harmonic frequencies. In addition, we investigate the suitability of the a posteriori scheme for molecular dynamics simulations, for which the analysis of the energy conservation constitutes a challenging tests. Our study demonstrates that the post-SCF approach in an excellent approximation.},
doi = {10.1063/1.4867195},
url = {https://www.osti.gov/biblio/22253484}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 18,
volume = 140,
place = {United States},
year = {Wed May 14 00:00:00 EDT 2014},
month = {Wed May 14 00:00:00 EDT 2014}
}