Circular dichroism in the photoelectron angular distribution of achiral molecules

Circular dichroism in the angular distribution (CDAD) is the effect that the angular intensity distribution of photoemitted electrons depends on the handedness of the incident circularly polarized light. The origin of CDAD can be manifold, including intrinsic properties of the system under study, such as chirality, spin-orbit interaction, or quantum-geometrical properties, but CDAD can also originate from final-state effects influenced by the experimental geometry. For example, CDAD has been reported for achiral organic molecules at the interface to metallic substrates. For this latter case, we investigate two prototypical π -conjugated molecules, namely, tetracene and pentacene, whose frontier orbitals have a similar shape but exhibit distinctly different symmetries. By comparing experimental CDAD momentum maps with simulations within time-dependent density functional theory, we show how the final state of the photoelectron must be regarded as the source of the CDAD in such otherwise achiral and quantum-geometrically trivial systems. We gain additional insight into the mechanism by employing a simple scattering model for the final state, which allows us to decompose the CDAD signal into partial wave contributions.