Chlorophylls (Chls) are known for fast, subpicosecond internal conversion (IC) from ultraviolet/blue absorbing ("B" or "Soret" states) to the energetically lower, red light-absorbing Q states. Consequently, excitation energy transfer (EET) in photosynthetic pigment-protein complexes involving the B states has so far not been considered. We present, for the first time, a theoretical framework for the existence of B-B EET in tightly coupled Chl aggregates such as photosynthetic pigment-protein complexes. We show that according to a Förster resonance energy transport (FRET) scheme, unmodulated B-B EET has an unexpectedly high range. Unsuppressed, it could pose an existential threat-the damage potential of blue light for photochemical reaction centers (RCs) is well-known. This insight reveals so-far undescribed roles for carotenoids (Crts, cf. previous article in this series) and Chl b (this article) of possibly vital importance. Our model system is the photosynthetic antenna pigment-protein complex (CP29). The focus of the study is on the role of Chl b for EET in the Q and B bands. Further, the initial excited pigment distribution in the B band is computed for relevant solar irradiation and wavelength-centered laser pulses. It is found that both accessory pigment classes compete efficiently with Chl a absorption in the B band, leaving only 40% of B band excitations for Chl a. B state population is preferentially relocated to Chl b after excitation of any Chls, due to a near-perfect match of Chl b B band absorption with Chl a B state emission spectra. This results in an efficient depletion of the Chl a population (0.66 per IC/EET step, as compared to 0.21 in a Chl a-only system). Since Chl b only occurs in the peripheral antenna complexes of plants and algae, and RCs contain only Chl a, this would automatically trap potentially dangerous B state population in the antennae, preventing forwarding to the RCs.

Department of Chemical Physics and Optics Charles University Ke Karlovu 3 121 16 Prague 2 Czech Republic

Institut für Chemie und Biochemie Fachbereich Biologie Chemie Pharmazie Freie Universität Berlin Arnimallee 22 14195 Berlin Germany

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Excitation Energy Transfer between Higher Excited States of Photosynthetic Pigments: 1. Carotenoids Intercept and Remove B Band Excitations