An effective potential for Frenkel excitons

Excitation energy transfer (EET) is a ubiquitous process in life and materials sciences. Here, a new and computationally efficient method of evaluating the electronic EET couplings between interacting chromophores is introduced that is valid in a wide range of intermolecular distances. The proposed approach is based on the effective elimination of electron repulsion integrals from the excitonic Hamiltonian matrix elements via the density-fitting approach and distributed multipole approximation. The excitonic Hamiltonian represented in a basis including charge transfer (CT) states is re-cast in terms of the effective one-electron potential functions (EOPs) and adapted into the effective fragment parameter (EFP) framework. Calculations for model systems indicate that the speedup of at least three orders of magnitude, as compared to the state-of-the-art methods, can be achieved while maintaining the accuracy of the EET couplings even at short intermolecular distances. EOP-TI - an approach for truly efficient calculations of both Förster and Dexter excitonic couplings.