ABSTRACTElectron transfer in molecular wires are of fundamental importance for a range of optoelectronic applications. The impact of electronic coherence and ionic vibrations on transmittance are of great importance to determine the mechanisms, and subsequently the type of wires that are most promising for applications. In this work, we use the real-time formulation of time-dependent density functional theory to study electron transfer through oligo-p-phenylenevinylene (OPV) and the recently synthesized carbon bridged counterpart (COPV). A system prototypical of organic photovoltaics is setup by bridging a porphyrin-fullerene dyad, allowing a photo-excited electron to flow between the Zn-porphyrin (ZnP) chromophore and the C60 electron acceptor through the molecular wire. The excited state is described using the fully self-consistent ∆-SCF method. The state is then propagated in time using the real-time TD-DFT scheme, while describing ionic vibrations with classical nuclei. The charge transferred between porphyrin and C60 is calculated and correlated with the velocity autocorrelation functions of the ions. This provides a microscopic insight to vibrational and tunneling contributions to electron transport in linked porphyrin-fullerene dyads. We elaborate on important details in describing the excited state and trajectory sampling.
The nature of frontier orbitals under systematic ligand exchange in (pseudo-)octahedral Fe(ii) complexes
