  Off-resonant charge transport through molecular junctions has been
extensively studied since the advent of single-molecule electronics and it is
now well understood within the framework of the non-interacting Landauer
approach. Conversely, gaining a qualitative and quantitative understanding of
the resonant transport regime has proven more elusive. Here, we study resonant
charge transport through graphene-based zinc-porphyrin junctions. We
experimentally demonstrate an inadequacy of the non-interacting Landauer theory
as well as the conventional single-mode Franck-Condon model. Instead, we model
the overall charge transport as a sequence of non-adiabatic electron transfers,
the rates of which depend on both outer and inner-sphere vibrational
interactions. We show that the transport properties of our molecular junctions
are determined by a combination of electron-electron and electron-vibrational
coupling, and are sensitive to the interactions with the wider local
environment. Furthermore, we assess the importance of nuclear tunnelling and
examine the suitability of semi-classical Marcus theory as a description of
charge transport in molecular devices.
