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Title: Photoinduced Intra- and Intermolecular Energy Transfer in Chlorophyll a Dimer

Abstract

By applying nonadiabatic excited-state molecular dynamics, we investigate excitation energy transfer and exciton localization dynamics in a chlorophyll a (Chla) dimer system at the interface of two monomers of light-harvesting complex II trimer. After its optical excitation at the red edge of the Soret (B) band, the Chla dimer experiences an ultrafast intra- and intermolecular nonradiative relaxation process to the lowest band (Qy). The energy relaxation is found to run faster in the Chla dimer than in the Chla monomer. Once the molecular system reaches the lowest Qy band composed of two lowest excited states S1 and S2, the concluding relaxation step involves the S2 → S1 population transfer, resulting in a relatively slower relaxation rate. The strength of thermal fluctuations exceeds intraband electronic coupling between the states belonging to a certain band (B, Qx, and Qy), producing localized states on individual chromophores. Therefore, time evolution of spatial electronic localization during internal conversion reveals transient trapping on one of the Chla monomers participating in the events of intermonomeric energy exchange. In the phase space domains where electronic states are strongly coupled, these states become nearly degenerate promoting Frenkel-exciton-like delocalization and interchromophore energy transfer. As energy relaxation occurs, redistribution of themore » transition density on two Chla monomers leads to nearly equal distribution of the exciton among the molecules. For a single Chla, our analysis of excitonic dynamics reveals wave function amplitude transfer from nitrogen and outer carbon atoms to inner carbon atoms during non-radiative relaxation.« less

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. Nanyang Technological Univ. (Singapore). Division of Materials Science
  2. National Univ. of Quilmes/CONICET, Bernal (Argentina)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Research Foundation (NRF) (Singapore); Ministry of Education (Singapore); National Scientific and Technical Research Council (CONICET) (Argentina); National Agency for Scientific and Technological Promotion (ANPCyT) (Argentina)
OSTI Identifier:
1460648
Report Number(s):
LA-UR-17-21993
Journal ID: ISSN 1520-6106; TRN: US1901887
Grant/Contract Number:  
AC52-06NA25396; NRF-CRP5-2009-04; RG106/15; PICT-2014-2662
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 121; Journal Issue: 21; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Zheng, Fulu, Fernandez-Alberti, Sebastian, Tretiak, Sergei, and Zhao, Yang. Photoinduced Intra- and Intermolecular Energy Transfer in Chlorophyll a Dimer. United States: N. p., 2017. Web. doi:10.1021/acs.jpcb.7b02021.
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Zheng, Fulu, Fernandez-Alberti, Sebastian, Tretiak, Sergei, & Zhao, Yang. Photoinduced Intra- and Intermolecular Energy Transfer in Chlorophyll a Dimer. United States. https://doi.org/10.1021/acs.jpcb.7b02021
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Zheng, Fulu, Fernandez-Alberti, Sebastian, Tretiak, Sergei, and Zhao, Yang. Mon . "Photoinduced Intra- and Intermolecular Energy Transfer in Chlorophyll a Dimer". United States. https://doi.org/10.1021/acs.jpcb.7b02021. https://www.osti.gov/servlets/purl/1460648.
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@article{osti_1460648,
title = {Photoinduced Intra- and Intermolecular Energy Transfer in Chlorophyll a Dimer},
author = {Zheng, Fulu and Fernandez-Alberti, Sebastian and Tretiak, Sergei and Zhao, Yang},
abstractNote = {By applying nonadiabatic excited-state molecular dynamics, we investigate excitation energy transfer and exciton localization dynamics in a chlorophyll a (Chla) dimer system at the interface of two monomers of light-harvesting complex II trimer. After its optical excitation at the red edge of the Soret (B) band, the Chla dimer experiences an ultrafast intra- and intermolecular nonradiative relaxation process to the lowest band (Qy). The energy relaxation is found to run faster in the Chla dimer than in the Chla monomer. Once the molecular system reaches the lowest Qy band composed of two lowest excited states S1 and S2, the concluding relaxation step involves the S2 → S1 population transfer, resulting in a relatively slower relaxation rate. The strength of thermal fluctuations exceeds intraband electronic coupling between the states belonging to a certain band (B, Qx, and Qy), producing localized states on individual chromophores. Therefore, time evolution of spatial electronic localization during internal conversion reveals transient trapping on one of the Chla monomers participating in the events of intermonomeric energy exchange. In the phase space domains where electronic states are strongly coupled, these states become nearly degenerate promoting Frenkel-exciton-like delocalization and interchromophore energy transfer. As energy relaxation occurs, redistribution of the transition density on two Chla monomers leads to nearly equal distribution of the exciton among the molecules. For a single Chla, our analysis of excitonic dynamics reveals wave function amplitude transfer from nitrogen and outer carbon atoms to inner carbon atoms during non-radiative relaxation.},
doi = {10.1021/acs.jpcb.7b02021},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 21,
volume = 121,
place = {United States},
year = {Mon May 08 00:00:00 EDT 2017},
month = {Mon May 08 00:00:00 EDT 2017}
}
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Works referenced in this record:

Molecular Mechanisms of Photosynthesis
book, December 2002

Natural strategies for photosynthetic light harvesting
journal, June 2014

  • Croce, Roberta; van Amerongen, Herbert
  • Nature Chemical Biology, Vol. 10, Issue 7
  • DOI: 10.1038/nchembio.1555

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
  • DOI: 10.1038/nchem.1145

Crystal structure of spinach major light-harvesting complex at 2.72 Å resolution
journal, March 2004

  • Liu, Zhenfeng; Yan, Hanchi; Wang, Kebin
  • Nature, Vol. 428, Issue 6980
  • DOI: 10.1038/nature02373

Chlorophyll arrangement in a bacteriochlorophyll protein from Chlorobium limicola
journal, December 1975

  • Fenna, R. E.; Matthews, B. W.
  • Nature, Vol. 258, Issue 5536
  • DOI: 10.1038/258573a0

Crystal structure of the bacteriochlorophyll a protein from Chlorobium tepidum 1 1Edited by R. Huber
journal, August 1997

  • Li, Yi-Fen; Zhou, Wenli; Blankenship, Robert E.
  • Journal of Molecular Biology, Vol. 271, Issue 3
  • DOI: 10.1006/jmbi.1997.1189

The 8.5 A projection map of the light-harvesting complex I from Rhodospirillum rubrum reveals a ring composed of 16 subunits.
journal, February 1995

Crystal structure of an integral membrane light-harvesting complex from photosynthetic bacteria
journal, April 1995

  • McDermott, G.; Prince, S. M.; Freer, A. A.
  • Nature, Vol. 374, Issue 6522
  • DOI: 10.1038/374517a0

The crystal structure of the light-harvesting complex II (B800–850) from Rhodospirillum molischianum
journal, May 1996

Energy transfer dynamics in trimers and aggregates of light-harvesting complex II probed by 2D electronic spectroscopy
journal, June 2015

  • Enriquez, Miriam M.; Akhtar, Parveen; Zhang, Cheng
  • The Journal of Chemical Physics, Vol. 142, Issue 21
  • DOI: 10.1063/1.4919239

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

Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A
journal, December 2015

  • Shenai, Prathamesh M.; Fernandez-Alberti, Sebastian; Bricker, William P.
  • The Journal of Physical Chemistry B, Vol. 120, Issue 1
  • DOI: 10.1021/acs.jpcb.5b09548

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

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

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

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

Ultrafast Photophysics and Photochemistry of [Ni]-Bacteriochlorophyll a
journal, August 1999

  • Musewald, Christian; Hartwich, Gerhard; Lossau, Harald
  • The Journal of Physical Chemistry B, Vol. 103, Issue 33
  • DOI: 10.1021/jp991388r

Ultrafast excited state dynamics of monomeric bacteriochlorophyll a
journal, December 2010

  • Kosumi, Daisuke; Maruta, Satoshi; Fujii, Ritsuko
  • physica status solidi (c), Vol. 8, Issue 1
  • DOI: 10.1002/pssc.201000684

Nonadiabatic Excited-State Molecular Dynamics Modeling of Photoinduced Dynamics in Conjugated Molecules
journal, May 2011

  • Nelson, Tammie; Fernandez-Alberti, Sebastian; Chernyak, Vladimir
  • The Journal of Physical Chemistry B, Vol. 115, Issue 18
  • DOI: 10.1021/jp109522g

Nonadiabatic Excited-State Molecular Dynamics: Modeling Photophysics in Organic Conjugated Materials
journal, February 2014

  • Nelson, Tammie; Fernandez-Alberti, Sebastian; Roitberg, Adrian E.
  • Accounts of Chemical Research, Vol. 47, Issue 4
  • DOI: 10.1021/ar400263p

Photoexcited Energy Transfer in a Weakly Coupled Dimer
journal, December 2014

  • Alfonso Hernandez, Laura; Nelson, Tammie; Tretiak, Sergei
  • The Journal of Physical Chemistry B, Vol. 119, Issue 24
  • DOI: 10.1021/jp510557f

Modeling of internal conversion in photoexcited conjugated molecular donors used in organic photovoltaics
journal, January 2014

  • Oldani, N.; Tretiak, S.; Bazan, G.
  • Energy & Environmental Science, Vol. 7, Issue 3
  • DOI: 10.1039/c3ee43170c

Self-Trapping of Excitons, Violation of Condon Approximation, and Efficient Fluorescence in Conjugated Cycloparaphenylenes
journal, October 2014

  • Adamska, Lyudmyla; Nayyar, Iffat; Chen, Hang
  • Nano Letters, Vol. 14, Issue 11
  • DOI: 10.1021/nl503133e

Computational Study of Photoexcited Dynamics in Bichromophoric Cross-Shaped Oligofluorene
journal, October 2014

  • Ondarse-Alvarez, D.; Oldani, N.; Tretiak, S.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 45
  • DOI: 10.1021/jp504720n

Molecular dynamics with electronic transitions
journal, July 1990

  • Tully, John C.
  • The Journal of Chemical Physics, Vol. 93, Issue 2
  • DOI: 10.1063/1.459170

Proton transfer in solution: Molecular dynamics with quantum transitions
journal, September 1994

  • Hammes‐Schiffer, Sharon; Tully, John C.
  • The Journal of Chemical Physics, Vol. 101, Issue 6
  • DOI: 10.1063/1.467455

Density Matrix Analysis and Simulation of Electronic Excitations in Conjugated and Aggregated Molecules
journal, September 2002

  • Tretiak, Sergei; Mukamel, Shaul
  • Chemical Reviews, Vol. 102, Issue 9
  • DOI: 10.1021/cr0101252

Krylov-space algorithms for time-dependent Hartree–Fock and density functional computations
journal, July 2000

  • Chernyak, Vladimir; Schulz, Michael F.; Mukamel, Shaul
  • The Journal of Chemical Physics, Vol. 113, Issue 1
  • DOI: 10.1063/1.481770

Representation independent algorithms for molecular response calculations in time-dependent self-consistent field theories
journal, February 2009

  • Tretiak, Sergei; Isborn, Christine M.; Niklasson, Anders M. N.
  • The Journal of Chemical Physics, Vol. 130, Issue 5
  • DOI: 10.1063/1.3068658

Adiabatic time-dependent density functional methods for excited state properties
journal, October 2002

  • Furche, Filipp; Ahlrichs, Reinhart
  • The Journal of Chemical Physics, Vol. 117, Issue 16
  • DOI: 10.1063/1.1508368

Resonant nonlinear polarizabilities in the time-dependent density functional theory
journal, November 2003

  • Tretiak, S.; Chernyak, V.
  • The Journal of Chemical Physics, Vol. 119, Issue 17
  • DOI: 10.1063/1.1614240

Electronic density-matrix algorithm for nonadiabatic couplings in molecular dynamics simulations
journal, January 2001

  • Tommasini, M.; Chernyak, V.; Mukamel, S.
  • International Journal of Quantum Chemistry, Vol. 85, Issue 4-5
  • DOI: 10.1002/qua.1528

Density-matrix representation of nonadiabatic couplings in time-dependent density functional (TDDFT) theories
journal, February 2000

  • Chernyak, Vladimir; Mukamel, Shaul
  • The Journal of Chemical Physics, Vol. 112, Issue 8
  • DOI: 10.1063/1.480511

Trees to trap photons
journal, July 1997

Electronic Coherence and Collective Optical Excitations of Conjugated Molecules
journal, August 1997

Recursive density‐matrix‐spectral‐moment algorithm for molecular nonlinear polarizabilities
journal, November 1996

  • Tretiak, Sergei; Chernyak, Vladimir; Mukamel, Shaul
  • The Journal of Chemical Physics, Vol. 105, Issue 19
  • DOI: 10.1063/1.472621

Excitonic couplings and electronic coherence in bridged naphthalene dimers
journal, November 1999

  • Tretiak, S.; Zhang, W. M.; Chernyak, V.
  • Proceedings of the National Academy of Sciences, Vol. 96, Issue 23
  • DOI: 10.1073/pnas.96.23.13003

Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular model
journal, June 1985

  • Dewar, Michael J. S.; Zoebisch, Eve G.; Healy, Eamonn F.
  • Journal of the American Chemical Society, Vol. 107, Issue 13
  • DOI: 10.1021/ja00299a024

Optimization of parameters for semiempirical methods IV: extension of MNDO, AM1, and PM3 to more main group elements
journal, April 2004

Multiconfiguration Self-Consistent Field and Multireference Configuration Interaction Methods and Applications
journal, December 2011

  • Szalay, Péter G.; Müller, Thomas; Gidofalvi, Gergely
  • Chemical Reviews, Vol. 112, Issue 1
  • DOI: 10.1021/cr200137a

An AM1 theoretical study of the structure and electronic properties of porphyrin
journal, December 1988

  • Reynolds, Charles H.
  • The Journal of Organic Chemistry, Vol. 53, Issue 26
  • DOI: 10.1021/jo00261a014

Electronic and structural properties of the metalloporphyrin structural isomers: semiempirical AM1 and PM3 calculations
journal, October 1997

Semi-empirical AM1 and PM3 calculations of five- and six-coordinate oxo iron (IV) porphyrin complexes
journal, September 2005

Optimization of parameters for semiempirical methods I. Method
journal, March 1989

Optimization of parameters for semiempirical methods II. Applications
journal, March 1989

Spectroscopic properties of Mg-chlorin, Mg-porphin and chlorophylls a, b, c1, c2, c3 and d studied by semi-empirical and ab initio MO/CI methods
journal, January 2000

  • Linnanto, Juha; Korppi-Tommola, Jouko
  • Physical Chemistry Chemical Physics, Vol. 2, Issue 21
  • DOI: 10.1039/b004998k

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

Analysis of Absorption Spectra of Zinc Porphyrin, Zinc m eso -Tetraphenylporphyrin, and Halogenated Derivatives
journal, September 2002

  • Nguyen, Kiet A.; Day, Paul N.; Pachter, Ruth
  • The Journal of Physical Chemistry A, Vol. 106, Issue 43
  • DOI: 10.1021/jp020053y

Nonadiabatic excited-state molecular dynamics: Numerical tests of convergence and parameters
journal, February 2012

  • Nelson, Tammie; Fernandez-Alberti, Sebastian; Chernyak, Vladimir
  • The Journal of Chemical Physics, Vol. 136, Issue 5
  • DOI: 10.1063/1.3680565

Multiscale Modeling of Electronic Excitations in Branched Conjugated Molecules Using an Exciton Scattering Approach
journal, February 2008

Exciton Hamiltonian for the Bacteriochlorophyll System in the LH2 Antenna Complex of Purple Bacteria
journal, May 2000

  • Tretiak, Sergei; Middleton, Chris; Chernyak, Vladimir
  • The Journal of Physical Chemistry B, Vol. 104, Issue 18
  • DOI: 10.1021/jp9939930

Bacteriochlorophyll and Carotenoid Excitonic Couplings in the LH2 System of Purple Bacteria
journal, October 2000

  • Tretiak, Sergei; Middleton, Chris; Chernyak, Vladimir
  • The Journal of Physical Chemistry B, Vol. 104, Issue 40
  • DOI: 10.1021/jp001585m

Spectra of porphyrins
journal, January 1961

Spectra of porphyrins
journal, January 1963

  • Gouterman, Martin; Wagnière, Georges H.; Snyder, Lawrence C.
  • Journal of Molecular Spectroscopy, Vol. 11, Issue 1-6
  • DOI: 10.1016/0022-2852(63)90011-0

Intra- and inter-monomeric transfers in the light harvesting LHCII complex: the Redfield–Förster picture
journal, January 2011

  • Novoderezhkin, Vladimir; Marin, Alessandro; van Grondelle, Rienk
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 38
  • DOI: 10.1039/c1cp21079c

Structure-Based Identification of Energy Sinks in Plant Light-Harvesting Complex II
journal, October 2010

  • Müh, Frank; Madjet, Mohamed El-Amine; Renger, Thomas
  • The Journal of Physical Chemistry B, Vol. 114, Issue 42
  • DOI: 10.1021/jp106323e
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