Coulomb interactions between dipolar quantum fluctuations in van der Waals bound molecules and materials

Mutual Coulomb interactions between electrons lead to a plethora of interesting physical and chemical effects, especially if those interactions involve many fluctuating electrons over large spatial scales. Here, we identify and study in detail the Coulomb interaction between dipolar quantum fluctuat...

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Bibliographic Details
Published in:Nature communications 2021-01, Vol.12 (1), p.137-9, Article 137
Main Authors: Stöhr, Martin, Sadhukhan, Mainak, Al-Hamdani, Yasmine S., Hermann, Jan, Tkatchenko, Alexandre
Format: Article
Language:English
Subjects:
119/118
639/638/563/606
639/638/563/979
639/638/563/980
639/766/94
Chemical effects
Computer applications
Dipoles
Dyes
Electron density
Fluctuations
Humanities and Social Sciences
multidisciplinary
Nanostructured materials
Science
Science (multidisciplinary)
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Summary:Mutual Coulomb interactions between electrons lead to a plethora of interesting physical and chemical effects, especially if those interactions involve many fluctuating electrons over large spatial scales. Here, we identify and study in detail the Coulomb interaction between dipolar quantum fluctuations in the context of van der Waals complexes and materials. Up to now, the interaction arising from the modification of the electron density due to quantum van der Waals interactions was considered to be vanishingly small. We demonstrate that in supramolecular systems and for molecules embedded in nanostructures, such contributions can amount to up to 6 kJ/mol and can even lead to qualitative changes in the long-range van der Waals interaction. Taking into account these broad implications, we advocate for the systematic assessment of so-called Dipole-Correlated Coulomb Singles in large molecular systems and discuss their relevance for explaining several recent puzzling experimental observations of collective behavior in nanostructured materials. High-level methods to describe van der Waals interactions are limited due to their computational cost. This work introduces a new theoretical approach, that extends the dipolar many-body dispersion formalism to higher-order contributions, demonstrated to be applicable to practically-relevant systems and nano-environments.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-020-20473-w