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

摘要

Theoretical prediction of transport and optical properties of protein-pigment complexes is of significant importance when aiming at understanding the structure versus 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 photo-active 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 (C. Curutchet, A. Muñoz-Losa, S. Monti, J. Kongsted, G. D. Scholes, and B. Mennucci, J. Chem. Theory Comput., 2009 5 (7), 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 including that explicit use of transition densities in the calculation of the electronic couplings - 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.