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

Abstract

Mutual Coulomb interactions between electrons lead to a plethora of\ninteresting physical and chemical effects, especially if those interactions\ninvolve many fluctuating electrons over large spatial scales. Here, we identify\nand study in detail the Coulomb interaction between dipolar quantum\nfluctuations in the context of van der Waals complexes and materials. Up to\nnow, the interaction arising from the modification of the electron density due\nto quantum van der Waals interactions was considered to be vanishingly small.\nWe demonstrate that in supramolecular systems and for molecules embedded in\nnanostructures, such contributions can amount to up to 6 kJ/mol and can even\nlead to qualitative changes in the long-range vdW interaction. Taking into\naccount these broad implications, we advocate for the systematic assessment of\nso-called Coulomb singles in large molecular systems and discuss their\nrelevance for explaining several recent puzzling experimental observations of\ncollective behavior in nanostructured materials.\n