Orientational Dependence of the van der Waals Interactions for Finite-Sized Particles

J Phys Chem A. 2018 May 17;122(19):4663-4669. doi: 10.1021/acs.jpca.8b01989. Epub 2018 May 3.

Abstract

Dispersion forces, especially van der Waals forces as interactions between neutral and polarizable particles act at small distances between two objects. Their theoretical origin lies in the electromagnetic interaction between induced dipole moments caused by the vacuum fluctuations of the ground-state electromagnetic field. The resulting theory well describes the experimental situation in the limit of the point dipole assumption. At smaller distances, where the finite size of the particles has to be taken into account, this description fails and has to be corrected by higher orders of the multipole expansion, such as quadrupole moments and so on. With respect to the complexity of the spatial properties of the particles this task requires a considerable effort. In order to describe the van der Waals interaction between such particles, we apply the established method of a spatially spread out polarizability distribution to approximate the higher orders of the multipole expansion. We thereby construct an effective theory for effects from anisotropy and finite size on the van der Waals potential.