Coarse-grained interaction potentials for polyaromatic hydrocarbons

Abstract

Using Kohn-Sham density functional theory (KS-DFT), we have studied the interaction between various polyaromatic hydrocarbon molecules. The systems range from mono-cyclic benzene up to hexabenzocoronene (hbc). For several conventional exchange-correlation functionals potential energy curves of interaction of the $π$-$π$ stacking hbc dimer are reported. It is found that all pure local density or generalized gradient approximated functionals yield qualitatively incorrect predictions regarding structure and interaction. Inclusion of a non-local, atom-centered correction to the KS-Hamiltonian enables quantitative predictions. The computed potential energy surfaces of interaction yield parameters for a coarse-grained potential, which can be employed to study discotic liquid-crystalline mesophases of derived polyaromatic macromolecules.