Charge separation in the photosystem II reaction center resolved by multispectral two-dimensional electronic spectroscopy

Nguyen, Hoang H.; Song, Yin; Maret, Elizabeth L.; Silori, Yogita; Willow, Rhiannon; Yocum, Charles F.; Ogilvie, Jennifer P.

doi:10.1126/sciadv.ade7190

Charge separation in the photosystem II reaction center resolved by multispectral two-dimensional electronic spectroscopy

Journal Article · Wed May 03 00:00:00 EDT 2023 · Science Advances

DOI:https://doi.org/10.1126/sciadv.ade7190· OSTI ID:2337769

^[1]; ^[2]; ^[3]; Silori, Yogita ^[3]; ^[3]; ^[3]; ^[3]

University of Michigan, Ann Arbor, MI (United States); University of Michigan
University of Michigan, Ann Arbor, MI (United States); Beijing Institute of Technology (China)
University of Michigan, Ann Arbor, MI (United States)

The photosystem II reaction center (PSII RC) performs the primary energy conversion steps of oxygenic photosynthesis. While the PSII RC has been studied extensively, the similar time scales of energy transfer and charge separation and the severely overlapping pigment transitions in the Qy region have led to multiple models of its charge separation mechanism and excitonic structure. Here, we combine two-dimensional electronic spectroscopy (2DES) with a continuum probe and two-dimensional electronic vibrational spectroscopy (2DEV) to study the cyt b559-D1D2 PSII RC at 77 K. This multispectral combination correlates the overlapping Qy excitons with distinct anion and pigment-specific Q_x and mid-infrared transitions to resolve the charge separation mechanism and excitonic structure. Through extensive simultaneous analysis of the multispectral 2D data, we find that charge separation proceeds on multiple time scales from a delocalized excited state via a single pathway in which Pheo_D1 is the primary electron acceptor, while Chl_D1 and P_D1 act in concert as the primary electron donor.

View Accepted Manuscript (DOE)

Research Organization:: University of Michigan, Ann Arbor, MI (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0016384

OSTI ID:: 2337769

Journal Information:: Science Advances, Journal Name: Science Advances Journal Issue: 18 Vol. 9; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

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charge separation
multidimensional spectroscopy
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