Vibronic Resonance Along Effective Modes Mediates Selective Energy Transfer in Excitonically Coupled Aggregates

Abstract

We recently proposed effective normal modes for excitonically coupled aggregates which exactly transform the energy transfer Hamiltonian into a sum of one-dimensional Hamiltonians along the effective normal modes. Identifying physically meaningful vibrational motions which maximally promote vibronic mixing suggested an interesting possibility of leveraging vibrational-electronic resonance for mediating selective energy transfer. Here we expand on the effective mode approach elucidating its iterative nature for successively larger aggregates, and extend the idea of mediated energy transfer to larger aggregates. We show that energy transfer between electronically uncoupled but vibronically resonant donor-acceptor sites does not depend on the intermediate site energy or the number of intermediate sites. The intermediate sites simply mediate electronic coupling such that vibronic coupling along specific promoter modes leads to direct donor-acceptor energy transfer bypassing any intermediate uphill energy transfer steps. We show that interplay between the electronic Hamiltonian and the effective mode transformation partitions the linear vibronic coupling along specific promoter modes to dictate the selectivity of mediated energy transfer, with a vital role of interference between vibronic couplings and multi-particle basis states. Our results suggest a general design principle for enhancing energy transfer through synergistic effects of vibronic resonance and weak mediated electronic coupling, where both effects individually do not promote efficient energy transfer. The effective mode approach proposed here paves a facile route towards four-wavemixing spectroscopy simulations of larger aggregates without severely approximating resonant vibronic coupling.