Ultrafast Energy Transfer Involving the Red Chlorophylls of Cyanobacterial Photosystem i Probed through Two-Dimensional Electronic Spectroscopy

Yumin Lee, Michael J. Gorka, John H. Golbeck, Jessica M. Anna

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Photosystem I (PSI) is a naturally occurring light-harvesting complex that drives oxygenic photosynthesis through a series of photoinitiated transmembrane electron transfer reactions that occur with a high quantum efficiency. Understanding the mechanism by which this process occurs is fundamental to understanding the near-unity quantum efficiency of PSI and in turn could lead to further insight into PSI-based technologies for solar energy conversion. In this article, we have applied two-dimensional electronic spectroscopy to PSI complexes isolated from two different cyanobacterial strains to gain further insight into the ultrafast energy transfer in PSI. The PSI complexes studied differ in the number and absorption of the red chlorophylls, chlorophylls that lie to lower energies than the reaction center. By applying a global analysis to the 2D electronic spectra of the PSI complexes we extract 2D decay associated spectra (2D-DAS). Through analysis of the 2D-DAS we observe a 50 fs relaxation among the bulk antenna chlorophylls in addition to two pathways of energy equilibration involving the red chlorophylls: a fast 200 fs equilibration followed by a 2-4 ps equilibration. As demonstrated with a model system, the 1, 3 coordinates of the cross-peaks in the 2D-DAS spectra indicate that the two equilibration pathways involve different chlorophyll molecules.

Original languageEnglish (US)
Pages (from-to)11631-11638
Number of pages8
JournalJournal of the American Chemical Society
Volume140
Issue number37
DOIs
StatePublished - Sep 19 2018

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Photosystem I Protein Complex
Energy Transfer
Chlorophyll
Energy transfer
Spectrum Analysis
Spectroscopy
Quantum efficiency
Photosynthesis
Solar Energy
Energy conversion
Solar energy
Complex Mixtures
Antennas
Molecules
Electrons
Technology
Light

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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title = "Ultrafast Energy Transfer Involving the Red Chlorophylls of Cyanobacterial Photosystem i Probed through Two-Dimensional Electronic Spectroscopy",
abstract = "Photosystem I (PSI) is a naturally occurring light-harvesting complex that drives oxygenic photosynthesis through a series of photoinitiated transmembrane electron transfer reactions that occur with a high quantum efficiency. Understanding the mechanism by which this process occurs is fundamental to understanding the near-unity quantum efficiency of PSI and in turn could lead to further insight into PSI-based technologies for solar energy conversion. In this article, we have applied two-dimensional electronic spectroscopy to PSI complexes isolated from two different cyanobacterial strains to gain further insight into the ultrafast energy transfer in PSI. The PSI complexes studied differ in the number and absorption of the red chlorophylls, chlorophylls that lie to lower energies than the reaction center. By applying a global analysis to the 2D electronic spectra of the PSI complexes we extract 2D decay associated spectra (2D-DAS). Through analysis of the 2D-DAS we observe a 50 fs relaxation among the bulk antenna chlorophylls in addition to two pathways of energy equilibration involving the red chlorophylls: a fast 200 fs equilibration followed by a 2-4 ps equilibration. As demonstrated with a model system, the 1, 3 coordinates of the cross-peaks in the 2D-DAS spectra indicate that the two equilibration pathways involve different chlorophyll molecules.",
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AU - Golbeck, John H.

AU - Anna, Jessica M.

PY - 2018/9/19

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N2 - Photosystem I (PSI) is a naturally occurring light-harvesting complex that drives oxygenic photosynthesis through a series of photoinitiated transmembrane electron transfer reactions that occur with a high quantum efficiency. Understanding the mechanism by which this process occurs is fundamental to understanding the near-unity quantum efficiency of PSI and in turn could lead to further insight into PSI-based technologies for solar energy conversion. In this article, we have applied two-dimensional electronic spectroscopy to PSI complexes isolated from two different cyanobacterial strains to gain further insight into the ultrafast energy transfer in PSI. The PSI complexes studied differ in the number and absorption of the red chlorophylls, chlorophylls that lie to lower energies than the reaction center. By applying a global analysis to the 2D electronic spectra of the PSI complexes we extract 2D decay associated spectra (2D-DAS). Through analysis of the 2D-DAS we observe a 50 fs relaxation among the bulk antenna chlorophylls in addition to two pathways of energy equilibration involving the red chlorophylls: a fast 200 fs equilibration followed by a 2-4 ps equilibration. As demonstrated with a model system, the 1, 3 coordinates of the cross-peaks in the 2D-DAS spectra indicate that the two equilibration pathways involve different chlorophyll molecules.

AB - Photosystem I (PSI) is a naturally occurring light-harvesting complex that drives oxygenic photosynthesis through a series of photoinitiated transmembrane electron transfer reactions that occur with a high quantum efficiency. Understanding the mechanism by which this process occurs is fundamental to understanding the near-unity quantum efficiency of PSI and in turn could lead to further insight into PSI-based technologies for solar energy conversion. In this article, we have applied two-dimensional electronic spectroscopy to PSI complexes isolated from two different cyanobacterial strains to gain further insight into the ultrafast energy transfer in PSI. The PSI complexes studied differ in the number and absorption of the red chlorophylls, chlorophylls that lie to lower energies than the reaction center. By applying a global analysis to the 2D electronic spectra of the PSI complexes we extract 2D decay associated spectra (2D-DAS). Through analysis of the 2D-DAS we observe a 50 fs relaxation among the bulk antenna chlorophylls in addition to two pathways of energy equilibration involving the red chlorophylls: a fast 200 fs equilibration followed by a 2-4 ps equilibration. As demonstrated with a model system, the 1, 3 coordinates of the cross-peaks in the 2D-DAS spectra indicate that the two equilibration pathways involve different chlorophyll molecules.

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