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

Abstract

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