On the Higher-Order Static Polarizabilities and Dispersion Coefficients of the Fullerenes: An Ab Initio Study

11 September 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

In this work, we used finite-field derivative techniques and density functional theory (DFT) to compute the static isotropic polarizability series (i.e., dipole, quadrupole, and octupole ) for the C60-C84 fullerenes and quantitatively assess the intrinsic non-additivity in these fundamental response properties. Critical analysis of the derived effective scaling laws provides new insight into how the electronic structure of finite-sized fullerenes---a unique dichotomy of electron confinement and delocalization effects due to their quasi-spherical cage-like structures and encapsulated void spaces---simultaneously limits and enhances their quantum mechanical response to electric field perturbations. Corresponding molecular dispersion coefficients needed to describe the non-trivial van der Waals (vdW) interactions in fullerene-based systems were obtained by inputting the polarizabilities into the hollow sphere model within the modified single-frequency approximation.
Using first-order perturbation theory in conjunction with >140,000 DFT calculations, we also computed the non-negligible zero-point vibrational contributions (zpvc) to the dipole polarizability in C60 and C70, thereby enabling direct comparison between theory and experiment for these quintessential nanostructures.

Keywords

polarizabilities
dispersion interactions
van der Waals
fullerenes
non-covalent interactions
non-bonded interactions

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