Coulomb Interactions between Dipolar Quantum Fluctuations in van der Waals Bound Molecules and Materials

TL;DR

This paper investigates Coulomb interactions between dipolar quantum fluctuations in van der Waals complexes, revealing significant contributions that can alter long-range interactions and explain experimental observations in nanostructured materials.

Contribution

It demonstrates that Coulomb interactions from quantum fluctuations are more substantial than previously thought, affecting molecular interactions and material properties.

Findings

Coulomb interactions can contribute up to 6 kJ/mol in certain systems.

Quantum fluctuation interactions can cause qualitative changes in van der Waals forces.

Relevance of Coulomb singles in explaining experimental phenomena in nanostructures.

Abstract

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 vdW interaction. Taking into account these broad implications, we advocate for the systematic assessment of so-called Coulomb singles in large molecular systems and discuss their relevance for explaining several recent puzzling experimental observations of collective behavior in nanostructured materials.