Control of Photoinduced Donor-to-Acceptor Transfer Yield with Polarized Light

Molecular species with near-degenerate excited states may be photoexcited into superpositions of these states with specific phase relationships. The subsequent photochemistry can depend on the nature of this superposition if the photochemistry proceeds more rapidly than when the phase relationship is lost. We explore the electron transfer dynamics initiated by circularly or linearly polarized excitation in near-degenerate excited state systems, and this approach is equally suited for describing electronic excitation energy transfer (e.g., Dexter) dynamics. We find that the electronic coupling pathway interference, product yields, and overall electronic dynamics are strongly influenced by the exciting light polarization when the electronic dynamics is more rapid than the decoherence of the excited-state superposition.