Understanding Experiments Through Simulated Photoinduced Electron Transfer: The Case of 1,3-Bis(3-perylenyl)propane

Photoinduced electron transfer reactions have been investigated for 1,3-bis(3-perylenyl)propane using a theoretical method that includes interactionsbetween multiple charge-configurations of the system and its coupling to its intramolecular phonon modes. Both charge separation and charge recombinationreactions are considered making it possible to compare relative lifetimes of specific states across different systems. Two different theories for calculating thecoupling between electronic states, Fock matrix recombination - bridge (FMR-B) and generalized Mulliken-Hush (GMH), are used to calculate all relevantcouplings between electronic states of the system. The couplings of each electronic state to the intramolecular vibrational modes are calculated based on aharmonic oscillator model, and everything is propagated in time using the Redfield equation. The dynamics predicted by either of the coupling methodsshow the same overall dynamics of the systems tested and comparison of experimental observations with the predicted dynamics exhibit good agreement.