Coarse-grained interaction potentials for polyaromatic hydrocarbons

TL;DR

This paper investigates the interaction potentials of polyaromatic hydrocarbons using density functional theory, highlighting the importance of non-local corrections for accurate predictions and providing parameters for coarse-grained modeling of liquid-crystalline phases.

Contribution

It introduces a method to compute accurate interaction potentials for polyaromatic hydrocarbons, emphasizing the role of non-local corrections in DFT.

Findings

Pure local and GGA functionals give incorrect interaction predictions.

Non-local corrections enable quantitative accuracy.

Potential parameters useful for modeling liquid-crystalline phases.

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 $\pi$-$\pi$ 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.