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  1. Free, publicly-accessible full text available June 9, 2023
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  3. Photosynthetic species evolved to protect their light-harvesting apparatus from photoxidative damage driven by intracellular redox conditions or environmental conditions. The Fenna–Matthews–Olson (FMO) pigment–protein complex from green sulfur bacteria exhibits redox-dependent quenching behavior partially due to two internal cysteine residues. Here, we show evidence that a photosynthetic complex exploits the quantum mechanics of vibronic mixing to activate an oxidative photoprotective mechanism. We use two-dimensional electronic spectroscopy (2DES) to capture energy transfer dynamics in wild-type and cysteine-deficient FMO mutant proteins under both reducing and oxidizing conditions. Under reducing conditions, we find equal energy transfer through the exciton 4–1 and 4–2-1 pathways becausemore »the exciton 4–1 energy gap is vibronically coupled with a bacteriochlorophyll-avibrational mode. Under oxidizing conditions, however, the resonance of the exciton 4–1 energy gap is detuned from the vibrational mode, causing excitons to preferentially steer through the indirect 4–2-1 pathway to increase the likelihood of exciton quenching. We use a Redfield model to show that the complex achieves this effect by tuning the site III energy via the redox state of its internal cysteine residues. This result shows how pigment–protein complexes exploit the quantum mechanics of vibronic coupling to steer energy transfer.

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  4. Transition metal dichalcogenides (TMDs) have attracted much interest in recent years due to their emerging material properties. In monolayer TMDs, such as MoS2, extreme quantum confinement is achieved in the monolayer limit. Although monolayer TMDs represent an ideal platform to explore excitonic physics using ultrafast spectroscopy, this exploration is currently limited by confusion regarding the origin of certain spectral features, including the below-bandgap PIA feature observed in pump-probe experiments. In this work, we document an absence of PIA features immediately after photoexcitation, indicating a lack of strong optically-induced biexciton formation. Below-bandgap PIA features are observed to grow in with amore »time constant of 110 ± 10 fs, indicative of other factors responsible for their origin. These results indicate that optically-induced biexciton formation is most likely not responsible for the previously observed PIA features in MoS2 monolayers.« less