Electronic Energy Transfer in Polarizable Heterogeneous Environments: A Systematic Investigation of Different Quantum Chemical Approaches.

Theoretical prediction of transport and optical properties of protein-pigment complexes is of significant importance when aiming at understanding the structure-function relationship in such systems. Electronic energy transfer (EET) couplings represent a key property in this respect since such couplings provide important insight into the strength of interaction between photoactive pigments in protein-pigment complexes. Recently, attention has been payed to how the environment modifies or even controls the electronic couplings. To enable such theoretical predictions, a fully polarizable embedding model has been suggested (Curutchet, C., et al. J. Chem. Theory Comput., 2009, 5, 1838-1848). In this work, we further develop this computational model by extending it with an ab initio derived polarizable force field including higher-order multipole moments. We use this extended model to systematically examine three different ways of obtaining EET couplings in a heterogeneous medium ranging from use of the exact transition density to a point-dipole approximation. Several interesting observations are made, for example, the explicit use of transition densities in the calculation of the electronic couplings, and also when including the explicit environment contribution, can be replaced by a much simpler transition point charge description without comprising the quality of the model predictions.