Tomographic identification of all molecular orbitals in a wide binding energy range

TL;DR

This paper demonstrates that photoemission orbital tomography (POT) can comprehensively identify all molecular orbitals over a wide energy range, providing detailed experimental data that benchmark and improve electronic structure calculations.

Contribution

The study introduces a method to experimentally identify all molecular orbitals over a large energy range using POT, and compares these results with DFT calculations to evaluate their accuracy.

Findings

POT can identify over 38 molecular orbitals in a single experiment.

The HSE hybrid functional best matches the experimental orbital energies.

Kohn-Sham orbitals closely approximate Dyson orbitals over a 10 eV energy range.

Abstract

In the past decade, photoemission orbital tomography (POT) has evolved into a powerful tool to investigate the electronic structure of organic molecules adsorbed on surfaces. Here we show that POT allows for the comprehensive experimental identification of all molecular orbitals in a substantial binding energy range, in the present case more than 10 eV. Making use of the angular distribution of photoelectrons as a function of binding energy, we exemplify this by extracting orbital-resolved partial densities of states (pDOS) for 15 $\pi$ and 23 $\sigma$ orbitals from the experimental photoemission intensities of the prototypical organic molecule bisanthene (C$_{28}$H$_{14}$) on a Cu(110) surface. In their entirety, these experimentally measured orbital-resolved pDOS for an essentially complete set of orbitals serve as a stringent benchmark for electronic structure methods, which we illustrate by performing density functional theory (DFT) calculations employing four frequently-used exchange-correlation functionals. By computing the respective molecular-orbital-projected densities of states of the bisanthene/Cu(110) interface, a one-to-one comparison with experimental data for an unprecedented number of 38 orbital energies becomes possible. The quantitative analysis of our data reveals that the range-separated hybrid functional HSE performs best for the investigated organic/metal interface. At a more fundamental level, the remarkable agreement between the experimental and the Kohn-Sham orbital energies over a binding energy range larger than 10\,eV suggests that -- perhaps unexpectedly -- Kohn-Sham orbitals approximate Dyson orbitals, which would rigorously account for the electron extraction process in photoemission spectroscopy but are notoriously difficult to compute, in a much better way than previously thought.