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Universal Pairwise Interatomic van der Waals Potentials Based on Quantum Drude Oscillators

[Image: see text] Repulsive short-range and attractive long-range van der Waals (vdW) forces play an appreciable role in the behavior of extended molecular systems. When using empirical force fields, the most popular computational methods applied to such systems, vdW forces are typically described b...

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Autores principales: Khabibrakhmanov, Almaz, Fedorov, Dmitry V., Tkatchenko, Alexandre
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10653113/
https://www.ncbi.nlm.nih.gov/pubmed/37875419
http://dx.doi.org/10.1021/acs.jctc.3c00797
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author Khabibrakhmanov, Almaz
Fedorov, Dmitry V.
Tkatchenko, Alexandre
author_facet Khabibrakhmanov, Almaz
Fedorov, Dmitry V.
Tkatchenko, Alexandre
author_sort Khabibrakhmanov, Almaz
collection PubMed
description [Image: see text] Repulsive short-range and attractive long-range van der Waals (vdW) forces play an appreciable role in the behavior of extended molecular systems. When using empirical force fields, the most popular computational methods applied to such systems, vdW forces are typically described by Lennard-Jones-like potentials, which unfortunately have a limited predictive power. Here, we present a universal parameterization of a quantum-mechanical vdW potential, which requires only two free-atom properties—the static dipole polarizability α(1) and the dipole–dipole C(6) dispersion coefficient. This is achieved by deriving the functional form of the potential from the quantum Drude oscillator (QDO) model, employing scaling laws for the equilibrium distance and the binding energy, and applying the microscopic law of corresponding states. The vdW–QDO potential is shown to be accurate for vdW binding energy curves, as demonstrated by comparing to the ab initio binding curves of 21 noble-gas dimers. The functional form of the vdW–QDO potential has the correct asymptotic behavior at both zero and infinite distances. In addition, it is shown that the damped vdW–QDO potential can accurately describe vdW interactions in dimers consisting of group II elements. Finally, we demonstrate the applicability of the atom-in-molecule vdW–QDO model for predicting accurate dispersion energies for molecular systems. The present work makes an important step toward constructing universal vdW potentials, which could benefit (bio)molecular computational studies.
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spelling pubmed-106531132023-11-16 Universal Pairwise Interatomic van der Waals Potentials Based on Quantum Drude Oscillators Khabibrakhmanov, Almaz Fedorov, Dmitry V. Tkatchenko, Alexandre J Chem Theory Comput [Image: see text] Repulsive short-range and attractive long-range van der Waals (vdW) forces play an appreciable role in the behavior of extended molecular systems. When using empirical force fields, the most popular computational methods applied to such systems, vdW forces are typically described by Lennard-Jones-like potentials, which unfortunately have a limited predictive power. Here, we present a universal parameterization of a quantum-mechanical vdW potential, which requires only two free-atom properties—the static dipole polarizability α(1) and the dipole–dipole C(6) dispersion coefficient. This is achieved by deriving the functional form of the potential from the quantum Drude oscillator (QDO) model, employing scaling laws for the equilibrium distance and the binding energy, and applying the microscopic law of corresponding states. The vdW–QDO potential is shown to be accurate for vdW binding energy curves, as demonstrated by comparing to the ab initio binding curves of 21 noble-gas dimers. The functional form of the vdW–QDO potential has the correct asymptotic behavior at both zero and infinite distances. In addition, it is shown that the damped vdW–QDO potential can accurately describe vdW interactions in dimers consisting of group II elements. Finally, we demonstrate the applicability of the atom-in-molecule vdW–QDO model for predicting accurate dispersion energies for molecular systems. The present work makes an important step toward constructing universal vdW potentials, which could benefit (bio)molecular computational studies. American Chemical Society 2023-10-24 /pmc/articles/PMC10653113/ /pubmed/37875419 http://dx.doi.org/10.1021/acs.jctc.3c00797 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Khabibrakhmanov, Almaz
Fedorov, Dmitry V.
Tkatchenko, Alexandre
Universal Pairwise Interatomic van der Waals Potentials Based on Quantum Drude Oscillators
title Universal Pairwise Interatomic van der Waals Potentials Based on Quantum Drude Oscillators
title_full Universal Pairwise Interatomic van der Waals Potentials Based on Quantum Drude Oscillators
title_fullStr Universal Pairwise Interatomic van der Waals Potentials Based on Quantum Drude Oscillators
title_full_unstemmed Universal Pairwise Interatomic van der Waals Potentials Based on Quantum Drude Oscillators
title_short Universal Pairwise Interatomic van der Waals Potentials Based on Quantum Drude Oscillators
title_sort universal pairwise interatomic van der waals potentials based on quantum drude oscillators
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10653113/
https://www.ncbi.nlm.nih.gov/pubmed/37875419
http://dx.doi.org/10.1021/acs.jctc.3c00797
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