Electronic structure of S-C6H5 self-assembled monolayers on Cu(111) and Au(111) substrates

TL;DR

This study employs first principles density functional theory to analyze the electronic structure of phenylthiolate self-assembled monolayers on Cu(111) and Au(111), revealing insights into their electronic properties and spectral characteristics.

Contribution

It provides detailed theoretical predictions of electronic states and spectra of phenylthiolate SAMs on metal substrates, enhancing understanding of their transport and spectral features.

Findings

Significant lateral dispersion of molecular states observed.

Calculated work functions and photoemission spectra match experimental data.

Predicted new electronic states not yet experimentally observed.

Abstract

We use first principles density functional theory to calculate the electronic structure of the phenylthiolate (S-C$_6$H$_5$) self-assembled monolayer (SAM) on Cu(111) and Au(111) substrates. We find significant lateral dispersion of the SAM molecular states and discuss its implications for transport properties of the molecular wire array. We calculate the two photon photoemission spectra and the work function of the SAM on Cu(111) and compare them with the available experimental data. Our results are used to discuss assignments of the observed spectral data and yield predictions for new electronic states due to the monolayer not yet accessed experimentally.