Comparison of two models for bridge-assisted charge transfer

Based on the reduced density matrix method, we compare two different approaches to calculate the dynamics of the electron transfer in systems with donor, bridge, and acceptor. In the first approach a vibrational substructure is taken into account for each electronic state and the corresponding states are displaced along a common reaction coordinate. In the second approach it is assumed that vibrational relaxation is much faster than the electron transfer and therefore the states are modeled by electronic levels only. In both approaches the system is coupled to a bath of harmonic oscillators but the way of relaxation is quite different. The theory is applied to the electron transfer in ${\rm H_2P}-{\rm ZnP}-{\rm Q}$ with free-base porphyrin (${\rm H_2P}$) being the donor, zinc porphyrin (${\rm ZnP}$) being the bridge and quinone (${\rm Q}$) the acceptor. The parameters are chosen as similar as possible for both approaches and the quality of the agreement is discussed.