Hermann, J;
Alfè, D;
Tkatchenko, A;
(2017)
Nanoscale π-π Stacked molecules are bound by collective charge fluctuations.
Nature Communications
, 8
, Article 14052. 10.1038/ncomms14052.
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Abstract
Non-covalent π-π interactions are central to chemical and biological processes, yet the full understanding of their origin that would unite the simplicity of empirical approaches with the accuracy of quantum calculations is still missing. Here we employ a quantum-mechanical Hamiltonian model for van der Waals interactions, to demonstrate that intermolecular electron correlation in large supramolecular complexes at equilibrium distances is appropriately described by collective charge fluctuations. We visualize these fluctuations and provide connections both to orbital-based approaches to electron correlation, as well as to the simple London pairwise picture. The reported binding energies of ten supramolecular complexes obtained from the quantum-mechanical fluctuation model joined with density functional calculations are within 5% of the reference energies calculated with the diffusion quantum Monte-Carlo method. Our analysis suggests that π-π stacking in supramolecular complexes can be characterized by strong contributions to the binding energy from delocalized, collective charge fluctuations-in contrast to complexes with other types of bonding.
| Type: | Article |
|---|---|
| Title: | Nanoscale π-π Stacked molecules are bound by collective charge fluctuations |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1038/ncomms14052 |
| Publisher version: | http://doi.org/10.1038/ncomms14052 |
| Language: | English |
| Additional information: | Copyright © 2017 The Author(s). All rights reserved. This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Earth Sciences |
| URI: | https://discovery.ucl.ac.uk/id/eprint/1542925 |
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