Ultrafast energy relaxation in single light-harvesting complexes

Maly, Pavel; Gruber, J. Michael; Cogdell, Richard J.; Mancal, Tomas; van Grondelle, Rienk

doi:10.1073/pnas.1522265113

Title: Ultrafast energy relaxation in single light-harvesting complexes

Journal Article · 22 February 2016 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.1522265113 · OSTI ID:1238807

Maly, Pavel ^[1]; Gruber, J. Michael ^[2]; Cogdell, Richard J. ^[3]; Mancal, Tomas ^[4]; van Grondelle, Rienk ^[2]

Vrije Univ. Amsterdam, Amsterdam (The Netherlands); Charles Univ. in Prague, Prague (Czech Republic)
Vrije Univ. Amsterdam, Amsterdam (The Netherlands)
Univ. of Glasgow, Glasgow (United Kingdom)
Charles Univ. in Prague, Prague (Czech Republic)

Energy relaxation in light-harvesting complexes has been extensively studied by various ultrafast spectroscopic techniques, the fastest processes being in the sub–100-fs range. At the same time, much slower dynamics have been observed in individual complexes by single-molecule fluorescence spectroscopy (SMS). In this work, we use a pump–probe-type SMS technique to observe the ultrafast energy relaxation in single light-harvesting complexes LH2 of purple bacteria. After excitation at 800 nm, the measured relaxation time distribution of multiple complexes has a peak at 95 fs and is asymmetric, with a tail at slower relaxation times. When tuning the excitation wavelength, the distribution changes in both its shape and position. The observed behavior agrees with what is to be expected from the LH2 excited states structure. As we show by a Redfield theory calculation of the relaxation times, the distribution shape corresponds to the expected effect of Gaussian disorder of the pigment transition energies. By repeatedly measuring few individual complexes for minutes, we find that complexes sample the relaxation time distribution on a timescale of seconds. Furthermore, by comparing the distribution from a single long-lived complex with the whole ensemble, we demonstrate that, regarding the relaxation times, the ensemble can be considered ergodic. Lastly, our findings thus agree with the commonly used notion of an ensemble of identical LH2 complexes experiencing slow random fluctuations.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Photosynthetic Antenna Research Center (PARC)

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

Grant/Contract Number:: SC0001035

OSTI ID:: 1238807

Alternate ID(s):: OSTI ID: 1387502

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Vol. 113, Issue 11; Related Information: PARC partners with Washington University in St. Louis (lead); University of California, Riverside; University of Glasgow, UK; Los Alamos National Laboratory; University of New Mexico; New Mexico Corsortium; North Carolina State University; Northwestern University; Oak Ridge National Laboratory; University of Pennsylvania; Sandia National Laboratories; University of Sheffield, UK; ISSN 0027-8424

Publisher:: National Academy of Sciences, Washington, DC (United States)Copyright Statement

Country of Publication:: United States

Language:: English

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