A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy
Abstract
Two dimensional electronic spectroscopy has proven to be a valuable experimental technique to reveal electronic excitation dynamics in photosynthetic pigment-protein complexes, nanoscale semiconductors, organic photovoltaic materials, and many other types of systems. It does not, however, provide direct information concerning the spatial structure and dynamics of excitons. 2D infrared spectroscopy has become a widely used tool for studying structural dynamics but is incapable of directly providing information concerning electronic excited states. 2D electronic-vibrational (2DEV) spectroscopy provides a link between these domains, directly connecting the electronic excitation with the vibrational structure of the system under study. In this work, we derive response functions for the 2DEV spectrum of a molecular dimer and propose a method by which 2DEV spectra could be used to directly measure the electronic site populations as a function of time following the initial electronic excitation. We present results from the response function simulations which show that our proposed approach is substantially valid. This method provides, to our knowledge, the first direct experimental method for measuring the electronic excited state dynamics in the spatial domain, on the molecular scale.
- Authors:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1407400
- Alternate Identifier(s):
- OSTI ID: 1229680
- Grant/Contract Number:
- AC02-05CH11231; AC03-76F000098
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 143; Journal Issue: 12; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 74 ATOMIC AND MOLECULAR PHYSICS
Citation Formats
Lewis, Nicholas H. C., Dong, Hui, Oliver, Thomas A. A., and Fleming, Graham R. A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy. United States: N. p., 2015.
Web. doi:10.1063/1.4931634.
Lewis, Nicholas H. C., Dong, Hui, Oliver, Thomas A. A., & Fleming, Graham R. A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy. United States. https://doi.org/10.1063/1.4931634
Lewis, Nicholas H. C., Dong, Hui, Oliver, Thomas A. A., and Fleming, Graham R. Mon .
"A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy". United States. https://doi.org/10.1063/1.4931634. https://www.osti.gov/servlets/purl/1407400.
@article{osti_1407400,
title = {A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy},
author = {Lewis, Nicholas H. C. and Dong, Hui and Oliver, Thomas A. A. and Fleming, Graham R.},
abstractNote = {Two dimensional electronic spectroscopy has proven to be a valuable experimental technique to reveal electronic excitation dynamics in photosynthetic pigment-protein complexes, nanoscale semiconductors, organic photovoltaic materials, and many other types of systems. It does not, however, provide direct information concerning the spatial structure and dynamics of excitons. 2D infrared spectroscopy has become a widely used tool for studying structural dynamics but is incapable of directly providing information concerning electronic excited states. 2D electronic-vibrational (2DEV) spectroscopy provides a link between these domains, directly connecting the electronic excitation with the vibrational structure of the system under study. In this work, we derive response functions for the 2DEV spectrum of a molecular dimer and propose a method by which 2DEV spectra could be used to directly measure the electronic site populations as a function of time following the initial electronic excitation. We present results from the response function simulations which show that our proposed approach is substantially valid. This method provides, to our knowledge, the first direct experimental method for measuring the electronic excited state dynamics in the spatial domain, on the molecular scale.},
doi = {10.1063/1.4931634},
journal = {Journal of Chemical Physics},
number = 12,
volume = 143,
place = {United States},
year = {Mon Sep 28 00:00:00 EDT 2015},
month = {Mon Sep 28 00:00:00 EDT 2015}
}
Web of Science
Works referenced in this record:
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
Third-order nonlinear optical response of energy transfer systems
journal, July 1999
- Yang, Mino; Fleming, Graham R.
- The Journal of Chemical Physics, Vol. 111, Issue 1
Two-Dimensional Electronic Spectroscopy of Molecular Aggregates
journal, September 2009
- Ginsberg, Naomi S.; Cheng, Yuan-Chung; Fleming, Graham R.
- Accounts of Chemical Research, Vol. 42, Issue 9
How Fissors Works: Observing Vibrationally Adiabatic Conformational Change through Femtosecond Stimulated Raman Spectroscopy
journal, May 2013
- Cina, Jeffrey A.; Kovac, Philip A.
- The Journal of Physical Chemistry A, Vol. 117, Issue 29
Impact of environmentally induced fluctuations on quantum mechanically mixed electronic and vibrational pigment states in photosynthetic energy transfer and 2D electronic spectra
journal, June 2015
- Fujihashi, Yuta; Fleming, Graham R.; Ishizaki, Akihito
- The Journal of Chemical Physics, Vol. 142, Issue 21
The fundamental role of quantized vibrations in coherent light harvesting by cryptophyte algae
journal, November 2012
- Kolli, Avinash; O’Reilly, Edward J.; Scholes, Gregory D.
- The Journal of Chemical Physics, Vol. 137, Issue 17
Vibronic coherence in oxygenic photosynthesis
journal, July 2014
- Fuller, Franklin D.; Pan, Jie; Gelzinis, Andrius
- Nature Chemistry, Vol. 6, Issue 8
Theoretical examination of quantum coherence in a photosynthetic system at physiological temperature
journal, October 2009
- Ishizaki, A.; Fleming, G. R.
- Proceedings of the National Academy of Sciences, Vol. 106, Issue 41
Modeling vibrational dephasing and energy relaxation of intramolecular anharmonic modes for multidimensional infrared spectroscopies
journal, August 2006
- Ishizaki, Akihito; Tanimura, Yoshitaka
- The Journal of Chemical Physics, Vol. 125, Issue 8
On the adequacy of the Redfield equation and related approaches to the study of quantum dynamics in electronic energy transfer
journal, June 2009
- Ishizaki, Akihito; Fleming, Graham R.
- The Journal of Chemical Physics, Vol. 130, Issue 23
Engineering Coherence Among Excited States in Synthetic Heterodimer Systems
journal, April 2013
- Hayes, D.; Griffin, G. B.; Engel, G. S.
- Science, Vol. 340, Issue 6139
Two-dimensional spectroscopy of a molecular dimer unveils the effects of vibronic coupling on exciton coherences
journal, January 2014
- Halpin, Alexei; Johnson, Philip J. M.; Tempelaar, Roel
- Nature Chemistry, Vol. 6, Issue 3
Spectroscopic elucidation of uncoupled transition energies in the major photosynthetic light-harvesting complex, LHCII
journal, July 2010
- Schlau-Cohen, G. S.; Calhoun, T. R.; Ginsberg, N. S.
- Proceedings of the National Academy of Sciences, Vol. 107, Issue 30
How Proteins Trigger Excitation Energy Transfer in the FMO Complex of Green Sulfur Bacteria
journal, October 2006
- Adolphs, Julia; Renger, Thomas
- Biophysical Journal, Vol. 91, Issue 8
Femtosecond Stimulated Raman Spectroscopy
journal, May 2007
- Kukura, Philipp; McCamant, David W.; Mathies, Richard A.
- Annual Review of Physical Chemistry, Vol. 58, Issue 1
A Structure-Based Model of Energy Transfer Reveals the Principles of Light Harvesting in Photosystem II Supercomplexes
journal, June 2013
- Bennett, Doran I. G.; Amarnath, Kapil; Fleming, Graham R.
- Journal of the American Chemical Society, Vol. 135, Issue 24
Determining the static electronic and vibrational energy correlations via two-dimensional electronic-vibrational spectroscopy
journal, May 2015
- Dong, Hui; Lewis, Nicholas H. C.; Oliver, Thomas A. A.
- The Journal of Chemical Physics, Vol. 142, Issue 17
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
A Femtosecond Visible/Visible and Visible/Mid-Infrared Transient Absorption Study of the Light Harvesting Complex II
journal, December 2009
- Stahl, Andreas D.; Di Donato, Mariangela; van Stokkum, Ivo
- Biophysical Journal, Vol. 97, Issue 12
Two-Dimensional Electronic Spectroscopy of Molecular Excitons
journal, September 2009
- Milota, Franz; Sperling, Jaroslaw; Nemeth, Alexandra
- Accounts of Chemical Research, Vol. 42, Issue 9
Photosynthetic Excitons
book, January 2000
- van Amerongen, Herbert; van Grondelle, Rienk; Valkunas, Leonas
- World Scientific
Theoretical Study of Time-Resolved Fluorescence Anisotropy from Coupled Chromophore Pairs
journal, March 1995
- Matro, Alexander; Cina, Jeffrey A.
- The Journal of Physical Chemistry, Vol. 99, Issue 9
Coherence Dynamics in Photosynthesis: Protein Protection of Excitonic Coherence
journal, June 2007
- Lee, H.; Cheng, Y. -C.; Fleming, G. R.
- Science, Vol. 316, Issue 5830
Cofactors Involved in Light-Driven Charge Separation in Photosystem I Identified by Subpicosecond Infrared Spectroscopy
journal, February 2011
- Di Donato, Mariangela; Stahl, Andreas D.; van Stokkum, Ivo H. M.
- Biochemistry, Vol. 50, Issue 4
Measuring correlated electronic and vibrational spectral dynamics using line shapes in two-dimensional electronic-vibrational spectroscopy
journal, May 2015
- Lewis, Nicholas H. C.; Dong, Hui; Oliver, Thomas A. A.
- The Journal of Chemical Physics, Vol. 142, Issue 17
A new algorithm for adaptive multidimensional integration
journal, May 1978
- Peter Lepage, G.
- Journal of Computational Physics, Vol. 27, Issue 2
On the Theory of Relaxation Processes
journal, January 1957
- Redfield, A. G.
- IBM Journal of Research and Development, Vol. 1, Issue 1
Ab Initio Nonadiabatic Dynamics of Multichromophore Complexes: A Scalable Graphical-Processing-Unit-Accelerated Exciton Framework
journal, July 2014
- Sisto, Aaron; Glowacki, David R.; Martinez, Todd J.
- Accounts of Chemical Research, Vol. 47, Issue 9
Direct evidence of quantum transport in photosynthetic light-harvesting complexes
journal, December 2011
- Panitchayangkoon, G.; Voronine, D. V.; Abramavicius, D.
- Proceedings of the National Academy of Sciences, Vol. 108, Issue 52
Following Coupled Electronic-Nuclear Motion through Conical Intersections in the Ultrafast Relaxation of β-Apo-8′-carotenal
journal, July 2015
- Oliver, Thomas A. A.; Fleming, Graham R.
- The Journal of Physical Chemistry B, Vol. 119, Issue 34
Solving structure in the CP29 light harvesting complex with polarization-phased 2D electronic spectroscopy
journal, February 2011
- Ginsberg, N. S.; Davis, J. A.; Ballottari, M.
- Proceedings of the National Academy of Sciences, Vol. 108, Issue 10
Concepts and Methods of 2D Infrared Spectroscopy
book, January 2011
- Hamm, Peter; Zanni, Martin
- Cambridge University Press
Correlating the motion of electrons and nuclei with two-dimensional electronic-vibrational spectroscopy
journal, June 2014
- Oliver, T. A. A.; Lewis, N. H. C.; Fleming, G. R.
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 28
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
Exciton Analysis in 2D Electronic Spectroscopy
journal, June 2005
- Cho, Minhaeng; Vaswani, Harsha M.; Brixner, Tobias
- The Journal of Physical Chemistry B, Vol. 109, Issue 21
Mapping the spatial overlap of excitons in a photosynthetic complex via coherent nonlinear frequency generation
journal, July 2011
- Dawlaty, Jahan M.; Bennett, Doran I. G.; Huxter, Vanessa M.
- The Journal of Chemical Physics, Vol. 135, Issue 4
Vibronic phenomena and exciton–vibrational interference in two-dimensional spectra of molecular aggregates
journal, January 2014
- Butkus, Vytautas; Valkunas, Leonas; Abramavicius, Darius
- The Journal of Chemical Physics, Vol. 140, Issue 3
Long-lived quantum coherence in photosynthetic complexes at physiological temperature
journal, July 2010
- Panitchayangkoon, G.; Hayes, D.; Fransted, K. A.
- Proceedings of the National Academy of Sciences, Vol. 107, Issue 29
The Theory of Relaxation Processes
book, January 1965
- Redfield, A. G.
- Advances in Magnetic Resonance
Quantum Coherence Enabled Determination of the Energy Landscape in Light-Harvesting Complex II
journal, December 2009
- Calhoun, Tessa R.; Ginsberg, Naomi S.; Schlau-Cohen, Gabriela S.
- The Journal of Physical Chemistry B, Vol. 113, Issue 51
Multiporphyrin Arrays with π–π Interchromophore Interactions
journal, December 2014
- Terazono, Yuichi; Kodis, Gerdenis; Chachisvilis, Mirianas
- Journal of the American Chemical Society, Vol. 137, Issue 1
Modelling Multi-Pulse Population Dynamics from Ultrafast Spectroscopy
journal, March 2011
- van Wilderen, Luuk J. G. W.; Lincoln, Craig N.; van Thor, Jasper J.
- PLoS ONE, Vol. 6, Issue 3
Synthesis of naphthalene-bridged porphyrin dimers and their orientation-dependent exciton coupling
journal, June 1988
- Osuka, Atsuhiro.; Maruyama, Kazuhiro.
- Journal of the American Chemical Society, Vol. 110, Issue 13
Quantum coherence in photosynthesis for efficient solar-energy conversion
journal, July 2014
- Romero, Elisabet; Augulis, Ramunas; Novoderezhkin, Vladimir I.
- Nature Physics, Vol. 10, Issue 9
Dynamics of a Multimode System Coupled to Multiple Heat Baths Probed by Two-Dimensional Infrared Spectroscopy †
journal, September 2007
- Ishizaki, Akihito; Tanimura, Yoshitaka
- The Journal of Physical Chemistry A, Vol. 111, Issue 38
The real‐time intramolecular electronic excitation transfer dynamics of 9’,9‐bifluorene and 2’,2‐binaphthyl in solution
journal, January 1993
- Zhu, F.; Galli, C.; Hochstrasser, R. M.
- The Journal of Chemical Physics, Vol. 98, Issue 2
Enhancement of Vibronic and Ground-State Vibrational Coherences in 2D Spectra of Photosynthetic Complexes
journal, June 2013
- Chenu, Aurélia; Christensson, Niklas; Kauffmann, Harald F.
- Scientific Reports, Vol. 3, Issue 1
The nature of coherences in the B820 bacteriochlorophyll dimer revealed by two-dimensional electronic spectroscopy
journal, January 2014
- Ferretti, Marco; Novoderezhkin, Vladimir I.; Romero, Elisabet
- Physical Chemistry Chemical Physics, Vol. 16, Issue 21
Memory effects in the relaxation of quantum open systems
journal, October 1992
- Suárez, Alberto; Silbey, Robert; Oppenheim, Irwin
- The Journal of Chemical Physics, Vol. 97, Issue 7
Dynamics of Light Harvesting in Photosynthesis
journal, May 2009
- Cheng, Yuan-Chung; Fleming, Graham R.
- Annual Review of Physical Chemistry, Vol. 60, Issue 1
Environment-assisted quantum transport
journal, March 2009
- Rebentrost, Patrick; Mohseni, Masoud; Kassal, Ivan
- New Journal of Physics, Vol. 11, Issue 3
Extracting the Excitonic Hamiltonian of the Fenna-Matthews-Olson Complex Using Three-Dimensional Third-Order Electronic Spectroscopy
journal, April 2011
- Hayes, Dugan; Engel, Gregory S.
- Biophysical Journal, Vol. 100, Issue 8
Quantum Coherence in Photosynthetic Light Harvesting
journal, March 2012
- Ishizaki, Akihito; Fleming, Graham R.
- Annual Review of Condensed Matter Physics, Vol. 3, Issue 1
Dynamics of Liquids, Molecules, and Proteins Measured with Ultrafast 2D IR Vibrational Echo Chemical Exchange Spectroscopy
journal, May 2009
- Fayer, M. D.
- Annual Review of Physical Chemistry, Vol. 60, Issue 1
Lessons from nature about solar light harvesting
journal, September 2011
- Scholes, Gregory D.; Fleming, Graham R.; Olaya-Castro, Alexandra
- Nature Chemistry, Vol. 3, Issue 10
Three-pulse photon echoes for model reactive systems
journal, June 1999
- Yang, Mino; Ohta, Kaoru; Fleming, Graham R.
- The Journal of Chemical Physics, Vol. 110, Issue 21
Herzberg–Teller Vibronic Coupling and the Duschinsky Effect
journal, April 1971
- Small, Gerald J.
- The Journal of Chemical Physics, Vol. 54, Issue 8
Spectroscopic characterization of the light-harvesting complex of Rhodospirillum rubrum and its structural subunit
journal, January 1990
- Chang, Mary C.; Callahan, Patricia M.; Parkes-Loach, Pamela S.
- Biochemistry, Vol. 29, Issue 2
Femtosecond Visible/Visible and Visible/Mid-IR Pump−Probe Study of the Photosystem II Core Antenna Complex CP47
journal, June 2004
- Groot, Marie Louise; Breton, Jacques; van Wilderen, Luuk J. G. W.
- The Journal of Physical Chemistry B, Vol. 108, Issue 23
Accounting for intra-molecular vibrational modes in open quantum system description of molecular systems
journal, November 2012
- Roden, Jan; Strunz, Walter T.; Whaley, K. Birgitta
- The Journal of Chemical Physics, Vol. 137, Issue 20
Integration of multiple chromophores with native photosynthetic antennas to enhance solar energy capture and delivery
journal, January 2013
- Harris, Michelle A.; Parkes-Loach, Pamela S.; Springer, Joseph W.
- Chemical Science, Vol. 4, Issue 10
Global and target analysis of time-resolved spectra
journal, July 2004
- van Stokkum, Ivo H. M.; Larsen, Delmar S.; van Grondelle, Rienk
- Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1657, Issue 2-3
Excited-State Dynamics of 8′-Apo-β-caroten-8′-al and 7′,7′-Dicyano-7′-apo-β-carotene Studied by Femtosecond Time-Resolved Infrared Spectroscopy
journal, October 2009
- Pang, Yoonsoo; Prantil, Matthew A.; Van Tassle, Aaron J.
- The Journal of Physical Chemistry B, Vol. 113, Issue 39
Femtosecond fluorescence depolarization study of photosynthetic antenna proteins: observation of ultrafast energy transfer in trimeric C-phycocyanin and allophycocyanin
conference, April 1992
- Xie, Sunney; Du, Mei; Mets, Laurens
- OE/LASE '92, SPIE Proceedings
Femtosecond Stimulated Raman Spectroscopy
journal, September 2006
- Kukura, Philipp; Yoon, Sangwoon; Mathies, Richard A.
- Analytical Chemistry, Vol. 78, Issue 17
Two-Dimensional Optical Spectroscopy
journal, December 2009
- Brauns, Eric B.
- Journal of the American Chemical Society, Vol. 132, Issue 3
Environment-Assisted Quantum Transport
text, January 2008
- Rebentrost, Patrick; Mohseni, Masoud; Kassal, Ivan
- arXiv
Impact of environmentally induced fluctuations on quantum mechanically mixed electronic and vibrational pigment states in photosynthetic energy transfer and 2D electronic spectra
text, January 2015
- Fujihashi, Yuta; Fleming, Graham R.; Ishizaki, Akihito
- arXiv
Works referencing / citing this record:
Ultrafast structural molecular dynamics investigated with 2D infrared spectroscopy methods
journal, October 2017
- Kraack, Jan Philip
- Topics in Current Chemistry, Vol. 375, Issue 6
Exploring ultraviolet photoinduced charge-transfer dynamics in a model dinucleotide of guanine and thymine
journal, January 2019
- Duchi, Marta; O’Hagan, Michael P.; Kumar, Rhea
- Physical Chemistry Chemical Physics, Vol. 21, Issue 26
Signatures of vibronic coupling in two-dimensional electronic-vibrational and vibrational-electronic spectroscopies
journal, September 2017
- Gaynor, James D.; Khalil, Munira
- The Journal of Chemical Physics, Vol. 147, Issue 9
Recent advances in multidimensional ultrafast spectroscopy
journal, January 2018
- Oliver, Thomas A. A.
- Royal Society Open Science, Vol. 5, Issue 1
Ultrafast structural molecular dynamics investigated with 2D infrared spectroscopy methods
book, October 2017
- Kraack, Jan Philip
- Topics in Current Chemistry Collections
Recent advances in multidimensional ultrafast spectroscopy
journal, January 2018
- Oliver, Thomas A. A.
- Royal Society Open Science, Vol. 5, Issue 1