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High-Pressure Modulation of Primary Photosynthetic Reactions

Research output: Contribution to journalArticle

Original languageEnglish
Number of pages24
JournalJournal of Physical Chemistry B
Volume2020
Early online date20 Jan 2020
DOIs
DateAccepted/In press - 9 Jan 2020
DateE-pub ahead of print (current) - 20 Jan 2020

Abstract

Photochemical charge separation is key to biological solar energy conversion.
Although many features of this highly quantum-efficient process have been described, others remain poorly understood. Herein, ultrafast fluorescence barospectroscopy is used for the first time to obtain insights into the mechanism of primary charge separation in a YM210W mutant bacterial reaction center under novel surrounding modulating conditions. Over a range of applied
hydrostatic pressures reaching 10 kbar the rate of primary charge separation monotonously increased and that of the electron transfer to secondary acceptor decreased. While the inferred free energy gap for charge separation generally narrowed with increasing pressure, a pressure-induced break of a protein-cofactor hydrogen bond observed at ~2 kbar significantly (by 219 cm–1 or 27
meV) increased this gap, resulting in a drop in fluorescence. The findings strongly favor a model for primary charge separation that incorporates charge recombination and restoration of the excited primary pair state, over a purely sequential model. We show that the main reason for the almost 3- fold acceleration of the primary electron transfer rate is the pressure-induced increase of the electronic coupling energy, rather than a change of activation energy. We also conclude that across all applied pressures the primary electron transfer in the mutant reaction center studied can be considered non-adiabatic, normal-region, and thermally activated.

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  • Full-text PDF (author’s accepted manuscript)

    Rights statement: This is the author accepted manuscript (AAM). The final published version (version of record) is available online via ACS Publications at https://doi.org/10.1021/acs.jpcb.9b09342 . Please refer to any applicable terms of use of the publisher.

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    Embargo ends: 9/01/21

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