Anisotropic molecular photoemission dynamics: Interpreting and accounting for the nuclear motion

Abstract

We investigate how vibration affects molecular photoemission dynamics, through simulations on two-dimension asymmetric model molecules including the electronic and nuclear motions in a fully correlated way. We show that a slight anisotropy in the electron-ion momentum sharing is sufficient to prevent one from unambigously characterizing the vibrationnaly averaged photoemission dynamics in terms of stereo Wigner delays. We further show that vibrational resolution can be retrieved in fixed-nuclei simulations, using effective molecular conformations that are specific to each vibrational channel. The optimal internuclear distances found empirically in 1-photon processes can be identified a priori using simple physical arguments. They also turn out to be efficient to simulate vibrationnally-resolved \rabbit measurements and to account for interchannel coherences in broadband 1-photon ionization.