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Title: Influence of weak vibrational-electronic couplings on 2D electronic spectra and inter-site coherence in weakly coupled photosynthetic complexes

Abstract

Coherence oscillations measured in two-dimensional (2D) electronic spectra of pigment-protein complexes may have electronic, vibrational, or mixed-character vibronic origins, which depend on the degree of electronic-vibrational mixing. Oscillations from intrapigment vibrations can obscure the inter-site coherence lifetime of interest in elucidating the mechanisms of energy transfer in photosynthetic light-harvesting. Huang-Rhys factors (S) for low-frequency vibrations in Chlorophyll and Bacteriochlorophyll are quite small (S ≤ 0.05), so it is often assumed that these vibrations influence neither 2D spectra nor inter-site coherence dynamics. In this work, we explore the influence of S within this range on the oscillatory signatures in simulated 2D spectra of a pigment heterodimer. To visualize the inter-site coherence dynamics underlying the 2D spectra, we introduce a formalism which we call the “site-probe response.” By comparing the calculated 2D spectra with the site-probe response, we show that an on-resonance vibration with Huang-Rhys factor as small as S = 0.005 and the most strongly coupled off-resonance vibrations (S = 0.05) give rise to long-lived, purely vibrational coherences at 77 K. We moreover calculate the correlation between optical pump interactions and subsequent entanglement between sites, as measured by the concurrence. At 77 K, greater long-lived inter-site coherence and entanglement appear withmore » increasing S. This dependence all but vanishes at physiological temperature, as environmentally induced fluctuations destroy the vibronic mixing.« less

Authors:
; ;  [1]
  1. Institute for Molecular Science, National Institutes of Natural Sciences, Okazaki 444-8585 (Japan)
Publication Date:
OSTI Identifier:
22493523
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 6; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHLOROPHYLL; COMPARATIVE EVALUATIONS; COMPLEXES; CORRELATIONS; ENERGY TRANSFER; FLUCTUATIONS; LIFETIME; MIXING; OSCILLATIONS; PIGMENTS; PROBES; TEMPERATURE DEPENDENCE; TWO-DIMENSIONAL SYSTEMS; VISIBLE RADIATION

Citation Formats

Monahan, Daniele M., Whaley-Mayda, Lukas, Fleming, Graham R., E-mail: grfleming@lbl.gov, Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Kavli Energy NanoSciences Institute at Berkeley, Berkeley, California 94720, and Ishizaki, Akihito. Influence of weak vibrational-electronic couplings on 2D electronic spectra and inter-site coherence in weakly coupled photosynthetic complexes. United States: N. p., 2015. Web. doi:10.1063/1.4928068.
Monahan, Daniele M., Whaley-Mayda, Lukas, Fleming, Graham R., E-mail: grfleming@lbl.gov, Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Kavli Energy NanoSciences Institute at Berkeley, Berkeley, California 94720, & Ishizaki, Akihito. Influence of weak vibrational-electronic couplings on 2D electronic spectra and inter-site coherence in weakly coupled photosynthetic complexes. United States. https://doi.org/10.1063/1.4928068
Monahan, Daniele M., Whaley-Mayda, Lukas, Fleming, Graham R., E-mail: grfleming@lbl.gov, Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Kavli Energy NanoSciences Institute at Berkeley, Berkeley, California 94720, and Ishizaki, Akihito. 2015. "Influence of weak vibrational-electronic couplings on 2D electronic spectra and inter-site coherence in weakly coupled photosynthetic complexes". United States. https://doi.org/10.1063/1.4928068.
@article{osti_22493523,
title = {Influence of weak vibrational-electronic couplings on 2D electronic spectra and inter-site coherence in weakly coupled photosynthetic complexes},
author = {Monahan, Daniele M. and Whaley-Mayda, Lukas and Fleming, Graham R., E-mail: grfleming@lbl.gov and Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 and Kavli Energy NanoSciences Institute at Berkeley, Berkeley, California 94720 and Ishizaki, Akihito},
abstractNote = {Coherence oscillations measured in two-dimensional (2D) electronic spectra of pigment-protein complexes may have electronic, vibrational, or mixed-character vibronic origins, which depend on the degree of electronic-vibrational mixing. Oscillations from intrapigment vibrations can obscure the inter-site coherence lifetime of interest in elucidating the mechanisms of energy transfer in photosynthetic light-harvesting. Huang-Rhys factors (S) for low-frequency vibrations in Chlorophyll and Bacteriochlorophyll are quite small (S ≤ 0.05), so it is often assumed that these vibrations influence neither 2D spectra nor inter-site coherence dynamics. In this work, we explore the influence of S within this range on the oscillatory signatures in simulated 2D spectra of a pigment heterodimer. To visualize the inter-site coherence dynamics underlying the 2D spectra, we introduce a formalism which we call the “site-probe response.” By comparing the calculated 2D spectra with the site-probe response, we show that an on-resonance vibration with Huang-Rhys factor as small as S = 0.005 and the most strongly coupled off-resonance vibrations (S = 0.05) give rise to long-lived, purely vibrational coherences at 77 K. We moreover calculate the correlation between optical pump interactions and subsequent entanglement between sites, as measured by the concurrence. At 77 K, greater long-lived inter-site coherence and entanglement appear with increasing S. This dependence all but vanishes at physiological temperature, as environmentally induced fluctuations destroy the vibronic mixing.},
doi = {10.1063/1.4928068},
url = {https://www.osti.gov/biblio/22493523}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 6,
volume = 143,
place = {United States},
year = {Fri Aug 14 00:00:00 EDT 2015},
month = {Fri Aug 14 00:00:00 EDT 2015}
}

Works referencing / citing this record:

Introduction to State-of-the-Art Multidimensional Time-Resolved Spectroscopy Methods
journal, June 2018


Coherent wavepackets in the Fenna–Matthews–Olson complex are robust to excitonic-structure perturbations caused by mutagenesis
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Effects of Herzberg–Teller vibronic coupling on coherent excitation energy transfer
journal, November 2016


Recent advances in multidimensional ultrafast spectroscopy
journal, January 2018


Coherent wavepackets in the Fenna-Matthews-Olson complex are robust to excitonic-structure perturbations caused by mutagenesis
journal, January 2019


Introduction to State-of-the-Art Multidimensional Time-Resolved Spectroscopy Methods
book, June 2018


Recent advances in multidimensional ultrafast spectroscopy
journal, January 2018