Dispersion Corrected DFT Study of Pentacene Thin Films on Flat and Vicinal Au Surfaces

TL;DR

This study uses dispersion-corrected DFT to analyze how pentacene thin films interact with flat and stepped gold surfaces, revealing the importance of Van der Waals forces and surface features in film structure and charge transfer.

Contribution

It provides a detailed comparison of dispersion-corrected and standard DFT methods in modeling pentacene on gold surfaces, highlighting the role of step edges and surface morphology.

Findings

Dispersion corrections significantly affect predicted molecular configurations.

Step edges enhance binding strength of pentacene molecules.

Vicinal surfaces promote better charge transport at the interface.

Abstract

Here we a present a density functional theory study of pentacene ultra-thin films on flat [(111)] and vicinal [(455)] Au surfaces. We have performed crystal and electronic structure calculations by using PBE and optB86b-vdW functionals and investigated the effects of long range Van der Waals interactions for different coverages starting from a single isolated molecule up to 4 monolayers of coverage. For an isolated molecule both functionals yield the hollow site as the most stable one with bridge-60 site being very close in energy in case of optB86b-vdW. Binding strength of an isolated pentacene on the step edge was found to be much larger than that on the terrace sites. Different experimentally reported monolayer structures were compared and the (6 x 3) unit cell was found to be energetically more stable than the (2 x 2 $\sqrt{7}$) and (2 x $\sqrt{31}$) ones. For one monolayer films while dispersion corrected calculations favored flat pentacene molecules on terraces, standard (PBE) calculations either found tilted and flat configurations to be energetically similar (on (111) surface) or favored the tilted configuration (on (455) surface). PDOS calculations performed with optB86b-vdW functional showed larger dispersion of molecular orbitals over the Au states for the (455) surface when compared with the (111) surface, indicating an enhanced charge carrier transport at the pentacene-gold interface in favor of the vicinal surface. Starting with the second monolayer, both functionals favored tilted configurations for both surfaces. Our results underline the importance of the dispersion corrections for the loosely bound systems like pentacene on gold and the role played by step edges in determining the multilayer film structure and charge transfer at the organic molecule-metal interface.