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Tailoring van der Waals dispersion interactions with external electric charges

van der Waals (vdW) dispersion interactions strongly impact the properties of molecules and materials. Often, the description of vdW interactions should account for the coupling with pervasive electric fields, stemming from membranes, ionic channels, liquids, or nearby charged functional groups. How...

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Detalles Bibliográficos
Autores principales: Kleshchonok, Andrii, Tkatchenko, Alexandre
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6070553/
https://www.ncbi.nlm.nih.gov/pubmed/30069005
http://dx.doi.org/10.1038/s41467-018-05407-x
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author Kleshchonok, Andrii
Tkatchenko, Alexandre
author_facet Kleshchonok, Andrii
Tkatchenko, Alexandre
author_sort Kleshchonok, Andrii
collection PubMed
description van der Waals (vdW) dispersion interactions strongly impact the properties of molecules and materials. Often, the description of vdW interactions should account for the coupling with pervasive electric fields, stemming from membranes, ionic channels, liquids, or nearby charged functional groups. However, this quantum-mechanical effect has been omitted in atomistic simulations, even in widely employed electronic-structure methods. Here, we develop a model and study the effects of an external charge on long-range vdW correlations. We show that a positive external charge stabilizes dispersion interactions, whereas a negative charge has an opposite effect. Our analytical results are benchmarked on a series of (bio)molecular dimers and supported by calculations with high-level correlated quantum-chemical methods, which estimate the induced dispersion to reach up to 35% of intermolecular binding energy (4 kT for amino-acid dimers at room temperature). Our analysis bridges electrostatic and electrodynamic descriptions of intermolecular interactions and may have implications for non-covalent reactions, exfoliation, dissolution, and permeation through biological membranes.
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spelling pubmed-60705532018-08-06 Tailoring van der Waals dispersion interactions with external electric charges Kleshchonok, Andrii Tkatchenko, Alexandre Nat Commun Article van der Waals (vdW) dispersion interactions strongly impact the properties of molecules and materials. Often, the description of vdW interactions should account for the coupling with pervasive electric fields, stemming from membranes, ionic channels, liquids, or nearby charged functional groups. However, this quantum-mechanical effect has been omitted in atomistic simulations, even in widely employed electronic-structure methods. Here, we develop a model and study the effects of an external charge on long-range vdW correlations. We show that a positive external charge stabilizes dispersion interactions, whereas a negative charge has an opposite effect. Our analytical results are benchmarked on a series of (bio)molecular dimers and supported by calculations with high-level correlated quantum-chemical methods, which estimate the induced dispersion to reach up to 35% of intermolecular binding energy (4 kT for amino-acid dimers at room temperature). Our analysis bridges electrostatic and electrodynamic descriptions of intermolecular interactions and may have implications for non-covalent reactions, exfoliation, dissolution, and permeation through biological membranes. Nature Publishing Group UK 2018-08-01 /pmc/articles/PMC6070553/ /pubmed/30069005 http://dx.doi.org/10.1038/s41467-018-05407-x Text en © The Author(s) 2018 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
spellingShingle Article
Kleshchonok, Andrii
Tkatchenko, Alexandre
Tailoring van der Waals dispersion interactions with external electric charges
title Tailoring van der Waals dispersion interactions with external electric charges
title_full Tailoring van der Waals dispersion interactions with external electric charges
title_fullStr Tailoring van der Waals dispersion interactions with external electric charges
title_full_unstemmed Tailoring van der Waals dispersion interactions with external electric charges
title_short Tailoring van der Waals dispersion interactions with external electric charges
title_sort tailoring van der waals dispersion interactions with external electric charges
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6070553/
https://www.ncbi.nlm.nih.gov/pubmed/30069005
http://dx.doi.org/10.1038/s41467-018-05407-x
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