Vibrational Modes Promoting Exciton Relaxation in the B850 Band of LH2

Jun Woo Kim; Tu C. Nguyen-Phan; Alastair T. Gardiner; Tai Hyun Yoon; Richard J. Cogdell; Minhaeng Cho; Gregory D. Scholes

doi:10.1021/acs.jpclett.1c03868

Vibrational Modes Promoting Exciton Relaxation in the B850 Band of LH2

Jun Woo Kim, Tu C. Nguyen-Phan, Alastair T. Gardiner, Tai Hyun Yoon, Richard J. Cogdell, Minhaeng Cho, Gregory D. Scholes

Research output: Contribution to journal › Article › peer-review

10 Citations (Scopus)

Abstract

Exciton relaxation dynamics in multichromophore systems are often modeled using Redfield theory, where bath fluctuations mediate the relaxation among the exciton eigenstates. Identifying the vibrational or phonon modes that are implicated in exciton relaxation allows more detailed understanding of exciton dynamics. Here we focus on a well-studied light-harvesting II complex (LH2) isolated from the photosynthetic purple bacterium Rhodoblastus acidophilus strain 10050. Using two synchronized mode-locked lasers, we carried out a polarization-dependent two-dimensional electronic spectroscopy (2DES) study of an ultrafast exciton relaxation in the B850 band of LH2. 2DES data with different polarization configurations enable us to investigate the exciton relaxation between the k = ±1 exciton states. Then, we identify vibrational modes coupled to the exciton relaxation by analyzing the coherent wavepackets in the 2DES signals. Focusing on the coherent vibrational wavepackets, the data suggest that certain symmetry-breaking modes of monomeric units play a key role in exciton relaxation.

Original language	English
Pages (from-to)	1099-1106
Number of pages	8
Journal	Journal of Physical Chemistry Letters
Volume	13
Issue number	4
DOIs	https://doi.org/10.1021/acs.jpclett.1c03868
Publication status	Published - 2022 Feb 3

Bibliographical note

Funding Information:
This material is based upon work supported by the U.S. Department of Energy, Office of Basic Energy Sciences under contract DE-SC0020437 (J.K. and G.D.S.) and the Institute for Basic Science in Korea (IBS-R23-D1, T.H.Y. and M.C.). T.C.N. and R.J.C. were supported by BBSRC grant n. BB/N0166734/1. A.T.G. and R.J.C. gratefully acknowledge funding from the Photosynthetic Antenna Research Center, an Energy Research Center funded by the Department of Energy, Office of Basic Energy Sciences, under award no. DE-SC0001035. All the experimental data were taken while J.K. visited the CMSD-IBS. We thank Dr. Noh Soo Hahn and Mr. Hyunmin Chang, who contributed to the maintenance of the frequency comb laser facility in the CMSD-IBS in Korea. We thank Professor Jeff Cina for discussions and comments on the manuscript.

Publisher Copyright:
©

ASJC Scopus subject areas

General Materials Science
Physical and Theoretical Chemistry

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10.1021/acs.jpclett.1c03868

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title = "Vibrational Modes Promoting Exciton Relaxation in the B850 Band of LH2",

abstract = "Exciton relaxation dynamics in multichromophore systems are often modeled using Redfield theory, where bath fluctuations mediate the relaxation among the exciton eigenstates. Identifying the vibrational or phonon modes that are implicated in exciton relaxation allows more detailed understanding of exciton dynamics. Here we focus on a well-studied light-harvesting II complex (LH2) isolated from the photosynthetic purple bacterium Rhodoblastus acidophilus strain 10050. Using two synchronized mode-locked lasers, we carried out a polarization-dependent two-dimensional electronic spectroscopy (2DES) study of an ultrafast exciton relaxation in the B850 band of LH2. 2DES data with different polarization configurations enable us to investigate the exciton relaxation between the k = ±1 exciton states. Then, we identify vibrational modes coupled to the exciton relaxation by analyzing the coherent wavepackets in the 2DES signals. Focusing on the coherent vibrational wavepackets, the data suggest that certain symmetry-breaking modes of monomeric units play a key role in exciton relaxation.",

author = "Kim, {Jun Woo} and Nguyen-Phan, {Tu C.} and Gardiner, {Alastair T.} and Yoon, {Tai Hyun} and Cogdell, {Richard J.} and Minhaeng Cho and Scholes, {Gregory D.}",

note = "Funding Information: This material is based upon work supported by the U.S. Department of Energy, Office of Basic Energy Sciences under contract DE-SC0020437 (J.K. and G.D.S.) and the Institute for Basic Science in Korea (IBS-R23-D1, T.H.Y. and M.C.). T.C.N. and R.J.C. were supported by BBSRC grant n. BB/N0166734/1. A.T.G. and R.J.C. gratefully acknowledge funding from the Photosynthetic Antenna Research Center, an Energy Research Center funded by the Department of Energy, Office of Basic Energy Sciences, under award no. DE-SC0001035. All the experimental data were taken while J.K. visited the CMSD-IBS. We thank Dr. Noh Soo Hahn and Mr. Hyunmin Chang, who contributed to the maintenance of the frequency comb laser facility in the CMSD-IBS in Korea. We thank Professor Jeff Cina for discussions and comments on the manuscript. Publisher Copyright: {\textcopyright} ",

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AU - Cogdell, Richard J.

AU - Cho, Minhaeng

AU - Scholes, Gregory D.

N1 - Funding Information: This material is based upon work supported by the U.S. Department of Energy, Office of Basic Energy Sciences under contract DE-SC0020437 (J.K. and G.D.S.) and the Institute for Basic Science in Korea (IBS-R23-D1, T.H.Y. and M.C.). T.C.N. and R.J.C. were supported by BBSRC grant n. BB/N0166734/1. A.T.G. and R.J.C. gratefully acknowledge funding from the Photosynthetic Antenna Research Center, an Energy Research Center funded by the Department of Energy, Office of Basic Energy Sciences, under award no. DE-SC0001035. All the experimental data were taken while J.K. visited the CMSD-IBS. We thank Dr. Noh Soo Hahn and Mr. Hyunmin Chang, who contributed to the maintenance of the frequency comb laser facility in the CMSD-IBS in Korea. We thank Professor Jeff Cina for discussions and comments on the manuscript. Publisher Copyright: ©

PY - 2022/2/3

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N2 - Exciton relaxation dynamics in multichromophore systems are often modeled using Redfield theory, where bath fluctuations mediate the relaxation among the exciton eigenstates. Identifying the vibrational or phonon modes that are implicated in exciton relaxation allows more detailed understanding of exciton dynamics. Here we focus on a well-studied light-harvesting II complex (LH2) isolated from the photosynthetic purple bacterium Rhodoblastus acidophilus strain 10050. Using two synchronized mode-locked lasers, we carried out a polarization-dependent two-dimensional electronic spectroscopy (2DES) study of an ultrafast exciton relaxation in the B850 band of LH2. 2DES data with different polarization configurations enable us to investigate the exciton relaxation between the k = ±1 exciton states. Then, we identify vibrational modes coupled to the exciton relaxation by analyzing the coherent wavepackets in the 2DES signals. Focusing on the coherent vibrational wavepackets, the data suggest that certain symmetry-breaking modes of monomeric units play a key role in exciton relaxation.

AB - Exciton relaxation dynamics in multichromophore systems are often modeled using Redfield theory, where bath fluctuations mediate the relaxation among the exciton eigenstates. Identifying the vibrational or phonon modes that are implicated in exciton relaxation allows more detailed understanding of exciton dynamics. Here we focus on a well-studied light-harvesting II complex (LH2) isolated from the photosynthetic purple bacterium Rhodoblastus acidophilus strain 10050. Using two synchronized mode-locked lasers, we carried out a polarization-dependent two-dimensional electronic spectroscopy (2DES) study of an ultrafast exciton relaxation in the B850 band of LH2. 2DES data with different polarization configurations enable us to investigate the exciton relaxation between the k = ±1 exciton states. Then, we identify vibrational modes coupled to the exciton relaxation by analyzing the coherent wavepackets in the 2DES signals. Focusing on the coherent vibrational wavepackets, the data suggest that certain symmetry-breaking modes of monomeric units play a key role in exciton relaxation.

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ER -

Vibrational Modes Promoting Exciton Relaxation in the B850 Band of LH2

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