Macroscopic Quantum Electrodynamics and Density Functional Theory Approaches to Dispersion Interactions between Fullerenes

Abstract

The processing and material properties of commercial organic semiconductors, for e.g. fullerenes is largely controlled by their precise arrangements, specially intermolecular symmetries, distances and orientations, more specifically, molecular polarisabilities. These supramolecular parameters heavily influence their electronic structure, thereby determining molecular photophysics and therefore dictating their usability as n-type semiconductors. In this article we evaluate van der Waals potentials of a fullerene dimer model system using two approaches: a) Density Functional Theory and, b) Macroscopic Quantum Electrodynamics, which is particularly suited for describing long-range van der Waals interactions. Essentially, we determine and explain the model symmetry, distance and rotational dependencies on binding energies and spectral changes. The resultant spectral tuning is compared using both methods showing correspondence within the constraints placed by the different model assumptions. We envision that the application of macroscopic methods and structure/property relationships laid forward in this article will find use in fundamental supramolecular electronics.

References in corpus (8)

• A real-space grid implementation of the Projector Augmented Wave method
• Progress in Time-Dependent Density-Functional Theory
• Casimir forces between arbitrary compact objects
• Numerical methods for computing Casimir interactions
• Quantum well states in two-dimensional gold clusters on MgO thin films
• Effective Polarisability Models
• Casimir-Polder interaction of fullerene molecules with surfaces
• Orientational dependence of the van der Waals interactions for finite-sized particles

Cited by in corpus (4)

• Effective screening of medium-assisted Van der Waals interactions between embedded particles
• Purcell-induced suppression of superradiance for molecular overlayers on noble atom surfaces
• Purcell modification of Auger and interatomic Coulombic decay
• Casimir energy for $N$ constant conductivity $\delta$-plates with a neural network perception