Ionization Pathway Interference in Photoionization Time Delays in Molecules.

The photoionization time-delay in linear conjugated molecules is computed using the Wigner scattering approach. We find that, in general, there are two additive contributions to the ionization time-delays. One originates from interferences between various ionization pathways that belong to different cationic eigenstates, while the other is due to time delays associated with each pathway and originates due to electron-electron correlations in the molecule. The former contribution scales up rapidly with the conjugation length, leading to larger time delays, as observed in recent experiments, while the latter is much less sensitive to the molecular conjugation.