Crucial Role of Nuclear Dynamics for Electron Injection in a Dye–Semiconductor Complex

We investigate the electron injection from a terrylene-based chromophore to the TiO2 semiconductor bridged by a recently proposed phenyl-amide-phenyl molecular rectifier. The mechanism of electron transfer is studied by means of quantum dynamics simulations using an extended Hückel Hamiltonian. It is found that the inclusion of the nuclear motion is necessary to observe the photoinduced electron transfer. In particular, the fluctuations of the dihedral angle between the terrylene and the phenyl ring modulate the localization and thus the electronic coupling between the donor and acceptor states involved in the injection process. The electron propagation shows characteristic oscillatory features that correlate with interatomic distance fluctuations in the bridge, which are associated with the vibrational modes driving the process. The understanding of such effects is important for the design of functional dyes with optimal injection and rectification properties.