Mapping charge-transfer excitations in Bacteriochlorophyll dimers from first principles

Photoinduced charge-transfer excitations are key to understand the primary processes of natural photosynthesis and for designing photovoltaic and photocatalytic devices. In this paper, we use Bacteriochlorophyll dimers extracted from the light harvesting apparatus and reaction center of a photosynthetic purple bacterium as model systems to study such excitations using first-principles numerical simulation methods. We distinguish four different regimes of intermolecular coupling, ranging from very weakly coupled to strongly coupled, and identify the factors that determine the energy and character of charge-transfer excitations in each case. We also construct an artificial dimer to systematically study the effects of intermolecular distance and orientation on charge-transfer excitations, as well as the impact of molecular vibrations on these excitations. Our results provide design rules for tailoring charge-transfer excitations in Bacteriochloropylls and related photoactive molecules, and highlight the importance of including charge-transfer excitations in accurate models of the excited-state structure and dynamics of Bacteriochlorophyll aggregates.