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Title: Two-dimensional electronic spectroscopy of a minimal photosystem I complex reveals the rate of primary charge separation
Authors: Akhtar, Parveen
Caspy, Ido
Nowakowski, Paweł J.
Malavath, Tirupathi
Nelson, Nathan
Tan, Howe-Siang
Lambrev, Petar H.
Keywords: Science::Chemistry
Issue Date: 2021
Source: Akhtar, P., Caspy, I., Nowakowski, P. J., Malavath, T., Nelson, N., Tan, H. & Lambrev, P. H. (2021). Two-dimensional electronic spectroscopy of a minimal photosystem I complex reveals the rate of primary charge separation. Journal of the American Chemical Society, 143(36), 14601-14612.
Project: RG2/19
Journal: Journal of the American Chemical Society
Abstract: Photosystem I (PSI), found in all oxygenic photosynthetic organisms, uses solar energy to drive electron transport with nearly 100% quantum efficiency, thanks to fast energy transfer among antenna chlorophylls and charge separation in the reaction center. There is no complete consensus regarding the kinetics of the elementary steps involved in the overall trapping, especially the rate of primary charge separation. In this work, we employed two-dimensional coherent electronic spectroscopy to follow the dynamics of energy and electron transfer in a monomeric PSI complex from Synechocystis PCC 6803, containing only subunits A-E, K, and M, at 77 K. We also determined the structure of the complex to 4.3 Å resolution by cryoelectron microscopy with refinements to 2.5 Å. We applied structure-based modeling using a combined Redfield-Förster theory to compute the excitation dynamics. The absorptive 2D electronic spectra revealed fast excitonic/vibronic relaxation on time scales of 50-100 fs from the high-energy side of the absorption spectrum. Antenna excitations were funneled within 1 ps to a small pool of chlorophylls absorbing around 687 nm, thereafter decaying with 4-20 ps lifetimes, independently of excitation wavelength. Redfield-Förster energy transfer computations showed that the kinetics is limited by transfer from these red-shifted pigments. The rate of primary charge separation, upon direct excitation of the reaction center, was determined to be 1.2-1.5 ps-1. This result implies activationless electron transfer in PSI.
ISSN: 0002-7863
DOI: 10.1021/jacs.1c05010
Rights: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see
Fulltext Permission: embargo_20220922
Fulltext Availability: With Fulltext
Appears in Collections:SPMS Journal Articles

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