STM Simulation of Molecules on Ultrathin Insulating Overlayers Using Tight-Binding: Au-Pentacene on NaCl bilayer on Cu

TL;DR

This paper introduces a fast tight-binding method for simulating STM images of molecules on ultrathin insulating layers, validated against experiments and DFT, revealing complex orbital shapes and phase shifts.

Contribution

The paper develops an efficient tight-binding approach for STM simulation of molecules on insulating overlayers, enabling analysis of phase shifts and complex orbital shapes.

Findings

TB method agrees with DFT and experimental data

Complex molecular orbitals can cause multivalued STM surfaces

Simulation reveals phase shifts in STM current

Abstract

We present a fast and efficient tight-binding (TB) method for simulating scanning tunneling microscopy (STM) imaging of adsorbate molecules on ultrathin insulating films. Due to the electronic decoupling of the molecule from the metal surface caused by the presence of the insulating overlayer, the STM images of the frontier molecular orbitals can be simulated using a very efficient scheme, which also enables the analysis of phase shifts in the STM current. Au-pentacene complex adsorbed on a NaCl bilayer on Cu substrate provides an intricate model system, which has been previously studied both experimentally and theoretically. Our calculations indicate that the complicated shape of the molecular orbitals may cause multivalued constant current surfaces -- leading to ambiguity of the STM image. The results obtained using the TB method are found to be consistent with both DFT calculations and experimental data.