Tailoring van der Waals dispersion interactions with external electric charges.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 30069005.
- Also identified by DOI 10.1038/s41467-018-05407-x and PMC identifier 6070553.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
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.