Can we use vibrational-excitonic resonance to control energy transfer?
David Jonas, University of Colorado Boulder
The standard Forster framework for understanding electronic energy transfer is based on the adiabatic approximation of slow vibrations and fast electrons. There is evidence that some natural processes involve resonant nonadiabatic vibrational-electronic coupling to delocalized vibrations. When the potential surface of the donor lies inside that of the acceptor, the resulting nested nonadiabatic funnel need not have a conical intersection, yet the adiabatic approximation can fail spectacularly over entire vibrational coordinate spaces, driving energy transfer outside the Forster framework. The nonadiabatic dynamics in nested funnels is efficient at low vibrational energies and does not require high vibrational velocities or conical intersections. The energy transfer dynamics involve tightly correlated changes in electronic and vibrational state. The width of the resonances is narrow, suggesting that one resonant acceptor can be selected. I will present a few results supporting this suggested control for a trimer.