Ultrafast molecular orbital tomography of a pentacene thin film using time-resolved momentum microscopy at a free-electron laser

Abstract Understanding and control of photon-induced dynamics of molecules on solid surfaces, including atomic rearrangements as well as charge transfer and non-equilibrium electron dynamics, are of essential importance for surface chemistry but also for the development of new devices. We use time-resolved momentum microscopy at a free-electron laser (FEL) and extend orbital tomography to time-resolved imaging of electronic wave functions of excited molecular orbitals. This technique will provide unprecedented insight into the ultrafast interplay between structural and electronic dynamics. In this work we prove general applicability and establish the experimental conditions at FEL sources to minimize space charge effects and radiation damage. We investigate a bilayer pentacene film on Ag(110) by optical laser pump and FEL probe experiments. From the momentum microscopy signal, we obtain time-dependent momentum maps of the molecular valence states that can be related to the molecular initial states by simulations of the involved photoemission matrix elements. A state above the Fermi level is identified which is temporarily occupied after optical excitation.