Van der Waals Coefficients for Nanostructures: Fullerenes Defy Conventional Wisdom

The van der Waals coefficients between quasispherical nanostructures can be modeled accurately and analytically by those of classical solid spheres (for nanoclusters) or spherical shells (for fullerenes) of uniform valence electron density, with the true static dipole polarizability. Here, we derive analytically and confirm numerically from this model the size dependencies of the van der Waals coefficients of all orders, showing, for example, that the asymptotic dependence for C-6 is the expected n(2) for pairs of nanoclusters A(n)-A(n), each containing n atoms, but n(2.75) for pairs of single-walled fullerenes C-n-C-n. Large fullerenes are argued to have much larger polarizabilities and dispersion coefficients than those predicted by either the standard atom pair-potential model or widely used nonlocal van der Waals correlation energy functionals.