Predicting photoemission intensities and angular distributions with real-time density-functional theory

Photoemission spectroscopy is one of the most frequently used tools for characterizing the electronic structure of condensed matter systems. We discuss a scheme for simulating photoemission from finite systems based on time-dependent density-functional theory. It allows for the first-principles calculation of relative electron binding energies, ionization cross sections, and anisotropy parameters. We extract these photoemission spectroscopy observables from Kohn-Sham orbitals propagated in real time. We demonstrate that the approach is capable of estimating photoemission intensities, i.e., peak heights. It can also reliably predict the angular distribution of photoelectrons. For the example of benzene we contrast calculated angular distribution anisotropy parameters to experimental reference data. Self-interaction free Kohn-Sham theory yields meaningful outer valence single-particle states in the right energetic order. We discuss how to properly choose the complex absorbing potential that is used in the simulations.