DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Vibronic structure of photosynthetic pigments probed by polarized two-dimensional electronic spectroscopy and ab initio calculations

Abstract

Using polarized 2D spectroscopy and state-of-the-art TDDFT calculations to uncover the vibronic structure of primary photosynthetic pigments and its effect on ultrafast photoexcited dynamics.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [4]; ORCiD logo [1]
  1. Department of Physics, University of Michigan, Ann Arbor, USA
  2. Department of Chemistry, University of Michigan, Ann Arbor, USA, Department of Chemistry and Biochemistry
  3. Applied Physics Program, University of Michigan, Ann Arbor, USA
  4. Department of Chemistry, University of Michigan, Ann Arbor, USA
  5. Department of Chemistry and Biochemistry, Kent State University, Kent, USA
Publication Date:
Research Org.:
Univ. of Michigan, Ann Arbor, MI (United States); Kent State Univ., Kent, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1543351
Alternate Identifier(s):
OSTI ID: 1612525; OSTI ID: 1773847
Grant/Contract Number:  
SC0016384; SC0016501; CHE-1362504; CHE-1464477; CHE-1800325
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 10 Journal Issue: 35; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 59 BASIC BIOLOGICAL SCIENCES; 14 SOLAR ENERGY; 74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Song, Yin, Schubert, Alexander, Maret, Elizabeth, Burdick, Ryan K., Dunietz, Barry D., Geva, Eitan, and Ogilvie, Jennifer P. Vibronic structure of photosynthetic pigments probed by polarized two-dimensional electronic spectroscopy and ab initio calculations. United Kingdom: N. p., 2019. Web. doi:10.1039/C9SC02329A.
Song, Yin, Schubert, Alexander, Maret, Elizabeth, Burdick, Ryan K., Dunietz, Barry D., Geva, Eitan, & Ogilvie, Jennifer P. Vibronic structure of photosynthetic pigments probed by polarized two-dimensional electronic spectroscopy and ab initio calculations. United Kingdom. https://doi.org/10.1039/C9SC02329A
Song, Yin, Schubert, Alexander, Maret, Elizabeth, Burdick, Ryan K., Dunietz, Barry D., Geva, Eitan, and Ogilvie, Jennifer P. Wed . "Vibronic structure of photosynthetic pigments probed by polarized two-dimensional electronic spectroscopy and ab initio calculations". United Kingdom. https://doi.org/10.1039/C9SC02329A.
@article{osti_1543351,
title = {Vibronic structure of photosynthetic pigments probed by polarized two-dimensional electronic spectroscopy and ab initio calculations},
author = {Song, Yin and Schubert, Alexander and Maret, Elizabeth and Burdick, Ryan K. and Dunietz, Barry D. and Geva, Eitan and Ogilvie, Jennifer P.},
abstractNote = {Using polarized 2D spectroscopy and state-of-the-art TDDFT calculations to uncover the vibronic structure of primary photosynthetic pigments and its effect on ultrafast photoexcited dynamics.},
doi = {10.1039/C9SC02329A},
journal = {Chemical Science},
number = 35,
volume = 10,
place = {United Kingdom},
year = {2019},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/C9SC02329A

Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Dichroism and polarized fluorescence of chlorophyll a, chlorophyll c and bacteriochlorophyll a dissolved in liquid crystals
journal, August 1980


Chlorophyll Spectra and Molecular Structure
journal, November 1955


Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature
journal, February 2010

  • Collini, Elisabetta; Wong, Cathy Y.; Wilk, Krystyna E.
  • Nature, Vol. 463, Issue 7281
  • DOI: 10.1038/nature08811

Exciton Structure and Energy Transfer in the Fenna–Matthews–Olson Complex
journal, April 2016

  • Thyrhaug, Erling; Žídek, Karel; Dostál, Jakub
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 9
  • DOI: 10.1021/acs.jpclett.6b00534

Temperature dependent activation energy for electron transfer between biological molecules
journal, June 1976

  • Jortner, Joshua
  • The Journal of Chemical Physics, Vol. 64, Issue 12
  • DOI: 10.1063/1.432142

Polarization-Controlled Two-Dimensional White-Light Spectroscopy of Semiconducting Carbon Nanotube Thin Films
journal, July 2016

  • Mehlenbacher, Randy D.; McDonough, Thomas J.; Kearns, Nicholas M.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 30
  • DOI: 10.1021/acs.jpcc.6b04961

Fluorescence Polarization of Some Porphyrins
journal, November 1962

  • Gouterman, Martin; Stryer, Lubert
  • The Journal of Chemical Physics, Vol. 37, Issue 10
  • DOI: 10.1063/1.1732996

Vibrational coherence probes the mechanism of ultrafast electron transfer in polymer–fullerene blends
journal, September 2014

  • Song, Yin; Clafton, Scott N.; Pensack, Ryan D.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5933

Vibronic coherence in oxygenic photosynthesis
journal, July 2014

  • Fuller, Franklin D.; Pan, Jie; Gelzinis, Andrius
  • Nature Chemistry, Vol. 6, Issue 8
  • DOI: 10.1038/nchem.2005

High-resolution optical spectra of chlorophyll molecules
journal, January 1985


Chapter 2. Physical methods and techniques. Part (iii) Ultraviolet and visible spectroscopy of bio-organic molecules
journal, January 1977


Tight-binding model of the photosystem II reaction center: application to two-dimensional electronic spectroscopy
journal, July 2013


Vibronic Origin of the Q y Absorption Tail of Bacteriochlorophyll a Verified by Fluorescence Excitation Spectroscopy and Quantum Chemical Simulations
journal, August 2017

  • Leiger, Kristjan; Linnanto, Juha Matti; Freiberg, Arvi
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 17
  • DOI: 10.1021/acs.jpclett.7b01704

Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems
journal, April 2007

  • Engel, Gregory S.; Calhoun, Tessa R.; Read, Elizabeth L.
  • Nature, Vol. 446, Issue 7137
  • DOI: 10.1038/nature05678

Chlorophylls, Symmetry, Chirality, and Photosynthesis
journal, September 2014

  • Senge, Mathias; Ryan, Aoife; Letchford, Kristie
  • Symmetry, Vol. 6, Issue 3
  • DOI: 10.3390/sym6030781

Comparison of pulse compression methods using only a pulse shaper
journal, January 2014

  • Wilcox, Daniel E.; Ogilvie, Jennifer P.
  • Journal of the Optical Society of America B, Vol. 31, Issue 7
  • DOI: 10.1364/JOSAB.31.001544

Density Functional Theory with Correct Long-Range Asymptotic Behavior
journal, February 2005


Two-Dimensional Electronic Spectroscopy of Chlorophyll a: Solvent Dependent Spectral Evolution
journal, June 2015

  • Moca, Roberta; Meech, Stephen R.; Heisler, Ismael A.
  • The Journal of Physical Chemistry B, Vol. 119, Issue 27
  • DOI: 10.1021/acs.jpcb.5b04339

Mechanistic insight into internal conversion process within Q-bands of chlorophyll a
journal, September 2017


Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014


Theoretical Study on Excited States of Bacteriochlorophyll a in Solutions with Density Functional Assessment
journal, September 2014

  • Higashi, Masahiro; Kosugi, Takahiro; Hayashi, Shigehiko
  • The Journal of Physical Chemistry B, Vol. 118, Issue 37
  • DOI: 10.1021/jp507259g

Understanding chlorophylls: Central magnesium ion and phytyl as structural determinants
journal, December 2008

  • Fiedor, Leszek; Kania, Agnieszka; Myśliwa-Kurdziel, Beata
  • Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1777, Issue 12
  • DOI: 10.1016/j.bbabio.2008.09.005

Properties of the excited singlet states of bacteriochlorophyll a and bacteriopheophytin a in polar solvents
journal, August 1991

  • Becker, Michael; Nagarajan, V.; Parson, William W.
  • Journal of the American Chemical Society, Vol. 113, Issue 18
  • DOI: 10.1021/ja00018a020

Low-temperature energy transfer in LHC-II trimers from the Chl a/b light-harvesting antenna of photosystem II
journal, May 1994


Quantum Mechanical Continuum Solvation Models
journal, August 2005

  • Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
  • Chemical Reviews, Vol. 105, Issue 8
  • DOI: 10.1021/cr9904009

Circular dichroism and magnetic circular dichroism of the chlorophyll and protochlorophyll pigments
journal, February 1970

  • Houssier, Claude.; Sauer, Kenneth.
  • Journal of the American Chemical Society, Vol. 92, Issue 4
  • DOI: 10.1021/ja00707a007

Multispectral multidimensional spectrometer spanning the ultraviolet to the mid-infrared
journal, January 2019

  • Song, Yin; Konar, Arkaprabha; Sechrist, Riley
  • Review of Scientific Instruments, Vol. 90, Issue 1
  • DOI: 10.1063/1.5055244

Dynamics of ground and excited state chlorophylla molecules in pyridine solution probed by femtosecond transient absorption spectroscopy
journal, August 1999


Compressor optimization with compressor-based multiphoton intrapulse interference phase scan (MIIPS)
journal, January 2012


Femtosecond spectroscopy study of electronically excited states of Chlorophyll a molecules in ethanol
journal, August 2003


Non-radiative relaxation of photoexcited chlorophylls: theoretical and experimental study
journal, September 2015

  • Bricker, William P.; Shenai, Prathamesh M.; Ghosh, Avishek
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep13625

Challenges facing an understanding of the nature of low-energy excited states in photosynthesis
journal, September 2016

  • Reimers, Jeffrey R.; Biczysko, Malgorzata; Bruce, Douglas
  • Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1857, Issue 9
  • DOI: 10.1016/j.bbabio.2016.06.010

Spectra of porphyrins
journal, January 1961


Optical Two-Dimensional Fourier Transform Spectroscopy of Semiconductor Quantum Wells
journal, September 2009

  • Cundiff, Steven T.; Zhang, Tianhao; Bristow, Alan D.
  • Accounts of Chemical Research, Vol. 42, Issue 9
  • DOI: 10.1021/ar9000636

Femtosecond spectroscopy of condensed phases with chirped supercontinuum probing
journal, March 1999


Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model
journal, March 1998

  • Barone, Vincenzo; Cossi, Maurizio
  • The Journal of Physical Chemistry A, Vol. 102, Issue 11
  • DOI: 10.1021/jp9716997

Cross-peak-specific two-dimensional electronic spectroscopy
journal, June 2007

  • Read, E. L.; Engel, G. S.; Calhoun, T. R.
  • Proceedings of the National Academy of Sciences, Vol. 104, Issue 36
  • DOI: 10.1073/pnas.0701201104

An ultrafast time-resolved anisotropy study of bacteriochlorophyll a in pyridine
journal, January 2000


Coherent Intrachain Energy Migration in a Conjugated Polymer at Room Temperature
journal, January 2009


Interaction of photosynthetic pigments with various organic solvents
journal, January 1999

  • Umetsu, Mitsuo; Wang, Zheng-Yu; Kobayashi, Masayuki
  • Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1410, Issue 1
  • DOI: 10.1016/S0005-2728(98)00170-4

Theoretical analysis of internal conversion pathways and vibrational relaxation process of chlorophyll-a in ethyl ether solvent
journal, May 2007


Two-dimensional IR-spectroscopy: polarization anisotropy effects
journal, May 2001


Sharp line vibronic spectra of chlorophyll and its derivatives in solid solutions
journal, June 1982


Exciton Superposition States in CdSe Nanocrystals Measured Using Broadband Two-Dimensional Electronic Spectroscopy
journal, January 2012

  • Turner, Daniel B.; Hassan, Yasser; Scholes, Gregory D.
  • Nano Letters, Vol. 12, Issue 2
  • DOI: 10.1021/nl2039502

Coupling Strength for Resonance Force Transfer of Electronic Energy in Van der Waals Solids
journal, March 1957

  • Simpson, William T.; Peterson, Don L.
  • The Journal of Chemical Physics, Vol. 26, Issue 3
  • DOI: 10.1063/1.1743351

Investigation of the internal conversion time of the chlorophyll a from S3, S2 to S1
journal, July 2005


Quantum Chemical Description of Absorption Properties and Excited-State Processes in Photosynthetic Systems
journal, November 2011


Optical absorption and electronic spectra of chlorophylls a and b
journal, January 2016

  • Hedayatifar, Leila; Irani, Elnaz; Mazarei, Mahmood
  • RSC Advances, Vol. 6, Issue 111
  • DOI: 10.1039/C6RA20226H

Direct observation of sub-picosecond equilibration of excitation energy in the light-harvesting antenna of Rhodospirillum rubrum
journal, September 1995


Visualization of Excitonic Structure in the Fenna-Matthews-Olson Photosynthetic Complex by Polarization-Dependent Two-Dimensional Electronic Spectroscopy
journal, July 2008

  • Read, Elizabeth L.; Schlau-Cohen, Gabriela S.; Engel, Gregory S.
  • Biophysical Journal, Vol. 95, Issue 2
  • DOI: 10.1529/biophysj.107.128199

Spectroscopic properties of photosystem II reaction center revisited
journal, September 2017

  • Gelzinis, Andrius; Abramavicius, Darius; Ogilvie, Jennifer P.
  • The Journal of Chemical Physics, Vol. 147, Issue 11
  • DOI: 10.1063/1.4997527

Evidence for 5- and 6-coordinated magnesium in bacteriochlorophyll a from visible absorption spectroscopy
journal, September 1975

  • Evans, Thomas A.; Katz, Joseph J.
  • Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 396, Issue 3
  • DOI: 10.1016/0005-2728(75)90147-4

Absorption-energy calculations of chlorophyll a and b with an explicit solvent model
journal, May 2018


Pulse shaping based two-dimensional electronic spectroscopy in a background free geometry
journal, January 2014

  • Fuller, Franklin D.; Wilcox, Daniel E.; Ogilvie, Jennifer P.
  • Optics Express, Vol. 22, Issue 1
  • DOI: 10.1364/OE.22.001018

Sub-20-fs pulses tunable across the visible from a blue-pumped single-pass noncollinear parametric converter
journal, January 1997


Density functional theory calculations of the visible spectrum of chlorophyll a
journal, March 1999


Assignment of the Q-Bands of the Chlorophylls: Coherence Loss via Qx − Qy Mixing
journal, September 2013

  • Reimers, Jeffrey R.; Cai, Zheng-Li; Kobayashi, Rika
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep02761

Self‐Consistent Molecular‐Orbital Methods. IX. An Extended Gaussian‐Type Basis for Molecular‐Orbital Studies of Organic Molecules
journal, January 1971

  • Ditchfield, R.; Hehre, W. J.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 54, Issue 2
  • DOI: 10.1063/1.1674902

An analysis of the visible absorption spectrum of chlorophyll a monomer, dimer, and oligomers in solution
journal, December 1976

  • Shipman, Lester L.; Cotton, Therese M.; Norris, James R.
  • Journal of the American Chemical Society, Vol. 98, Issue 25
  • DOI: 10.1021/ja00441a056

Mirror symmetry and vibrational structure in optical spectra of chlorophyll a
journal, May 2009

  • Rätsep, Margus; Linnanto, Juha; Freiberg, Arvi
  • The Journal of Chemical Physics, Vol. 130, Issue 19
  • DOI: 10.1063/1.3125183

Generation of <7 fs pulses at 800 nm from a blue-pumped optical parametric amplifier at degeneracy
journal, January 2009


Fundamental Gaps of Condensed-Phase Organic Semiconductors from Single-Molecule Calculations using Polarization-Consistent Optimally Tuned Screened Range-Separated Hybrid Functionals
journal, November 2018

  • Bhandari, Srijana; Cheung, Margaret S.; Geva, Eitan
  • Journal of Chemical Theory and Computation, Vol. 14, Issue 12
  • DOI: 10.1021/acs.jctc.8b00876

Molecular Dynamics Simulation Study of Chlorophyll a in Different Organic Solvents
journal, February 2011

  • Karki, Khadga; Roccatano, Danilo
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 4
  • DOI: 10.1021/ct1004627

Femtosecond pump-probe spectroscopy of bacteriochlorophyll a monomers in solution
journal, November 1994


Broadband 2D Electronic Spectroscopy Reveals a Carotenoid Dark State in Purple Bacteria
journal, April 2013

  • Ostroumov, Evgeny E.; Mulvaney, Rachel M.; Cogdell, Richard J.
  • Science, Vol. 340, Issue 6128
  • DOI: 10.1126/science.1230106

Ultrafast intramolecular relaxation dynamics of Mg- and Zn-bacteriochlorophyll a
journal, July 2013

  • Kosumi, Daisuke; Nakagawa, Katsunori; Sakai, Shunsuke
  • The Journal of Chemical Physics, Vol. 139, Issue 3
  • DOI: 10.1063/1.4813526

Three-Dimensional Orientation of the Q y Electronic Transition Dipole Moment within the Chlorophyll a Molecule Determined by Femtosecond Polarization Resolved VIS Pump−IR Probe Spectroscopy
journal, November 2008

  • Linke, Martin; Lauer, Alexandra; von Haimberger, Theodore
  • Journal of the American Chemical Society, Vol. 130, Issue 45
  • DOI: 10.1021/ja804096s

Laser action and excited state absorption of chlorophyll-a
journal, February 1977


Quantitative Prediction of Optical Absorption in Molecular Solids from an Optimally Tuned Screened Range-Separated Hybrid Functional
journal, May 2018

  • Manna, Arun K.; Refaely-Abramson, Sivan; Reilly, Anthony M.
  • Journal of Chemical Theory and Computation, Vol. 14, Issue 6
  • DOI: 10.1021/acs.jctc.7b01058

Calculation from First Principles of Intramolecular Golden-Rule Rate Constants for Photo-Induced Electron Transfer in Molecular Donor–Acceptor Systems
journal, October 2013

  • Lee, Myeong H.; Dunietz, Barry D.; Geva, Eitan
  • The Journal of Physical Chemistry C, Vol. 117, Issue 44
  • DOI: 10.1021/jp4081417

Two-Dimensional Electronic-Vibrational Spectroscopy of Chlorophyll a and b
journal, February 2016

  • Lewis, Nicholas H. C.; Fleming, Graham R.
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 5
  • DOI: 10.1021/acs.jpclett.6b00037

Demonstration and interpretation of significant asymmetry in the low-resolution and high-resolution Q y fluorescence and absorption spectra of bacteriochlorophyll a
journal, January 2011

  • Rätsep, Margus; Cai, Zheng-Li; Reimers, Jeffrey R.
  • The Journal of Chemical Physics, Vol. 134, Issue 2
  • DOI: 10.1063/1.3518685

Two-dimensional spectroscopy of electronic couplings in photosynthesis
journal, March 2005

  • Brixner, Tobias; Stenger, Jens; Vaswani, Harsha M.
  • Nature, Vol. 434, Issue 7033
  • DOI: 10.1038/nature03429

Two-dimensional electronic spectroscopy of bacteriochlorophyll a in solution: Elucidating the coherence dynamics of the Fenna-Matthews-Olson complex using its chromophore as a control
journal, September 2012

  • Fransted, Kelly A.; Caram, Justin R.; Hayes, Dugan
  • The Journal of Chemical Physics, Vol. 137, Issue 12
  • DOI: 10.1063/1.4752107

Solid-state optical absorption from optimally tuned time-dependent range-separated hybrid density functional theory
journal, August 2015


Resolving the ambiguity in the relation between Stokes shift and Huang–Rhys parameter
journal, January 2015

  • de Jong, Mathijs; Seijo, Luis; Meijerink, Andries
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 26
  • DOI: 10.1039/C5CP02093J

Theoretical study of vibrational relaxation and internal conversion dynamics of chlorophyll-a in ethyl acetate solvent in femtosecond laser fields
journal, December 2006


Quantum chemical simulation of excited states of chlorophylls, bacteriochlorophylls and their complexes
journal, January 2006

  • Linnanto, Juha; Korppi-Tommola, Jouko
  • Phys. Chem. Chem. Phys., Vol. 8, Issue 6
  • DOI: 10.1039/B513086G

The Pi electron structure and absorption spectra of chlorophylls in solution
journal, October 1972


Bacteriochlorophyll electronic transition moment directions in bacteriochlorophyll a-protein
journal, October 1978

  • Pearlstein, R. M.; Hemenger, R. P.
  • Proceedings of the National Academy of Sciences, Vol. 75, Issue 10
  • DOI: 10.1073/pnas.75.10.4920

Exciton−Exciton Correlations Revealed by Two-Quantum, Two-Dimensional Fourier Transform Optical Spectroscopy
journal, September 2009

  • Stone, Katherine W.; Turner, Daniel B.; Gundogdu, Kenan
  • Accounts of Chemical Research, Vol. 42, Issue 9
  • DOI: 10.1021/ar900122k

Measuring the Spectral Diffusion of Chlorophyll a Using Two-Dimensional Electronic Spectroscopy
journal, February 2013

  • Wells, Kym L.; Zhang, Zhengyang; Rouxel, Jérémy R.
  • The Journal of Physical Chemistry B, Vol. 117, Issue 8
  • DOI: 10.1021/jp310154y

Interaction of photosynthetic pigments with various organic solvents 2
journal, April 2000

  • Umetsu, Mitsuo; Wang, Zheng-Yu; Yoza, Kenzi
  • Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1457, Issue 3
  • DOI: 10.1016/S0005-2728(00)00070-0

Coherent wavepackets in the Fenna–Matthews–Olson complex are robust to excitonic-structure perturbations caused by mutagenesis
journal, January 2018

  • Maiuri, Margherita; Ostroumov, Evgeny E.; Saer, Rafael G.
  • Nature Chemistry, Vol. 10, Issue 2
  • DOI: 10.1038/nchem.2910

Works referencing / citing this record:

Discovery and characterization of an acridine radical photoreductant
journal, April 2020