Emission lineshapes of the B850 band of light-harvesting 2 (LH2) complex in purple bacteria: A second order time-nonlocal quantum master equation approach

Kumar, Praveen; Jang, Seogjoo

doi:10.1063/1.4795824

Emission lineshapes of the B850 band of light-harvesting 2 (LH2) complex in purple bacteria: A second order time-nonlocal quantum master equation approach

Journal Article · Sun Apr 07 00:00:00 EDT 2013 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4795824· OSTI ID:1751947

Kumar, Praveen ^[1]; Jang, Seogjoo ^[2]

City Univ. of New York (CUNY), NY (United States); Queens College, City University of New York
City Univ. of New York (CUNY), NY (United States)

The emission lineshape of the B850 band in the light harvesting complex 2 of purple bacteria is calculated by extending the approach of 2nd order time-nonlocal quantum master equation [S. Jang and R. J. Silbey, J. Chem. Phys. 118, 9312 (2003)]. The initial condition for the emission process corresponds to the stationary excited state density where exciton states are entangled with the bath modes in equilibrium. This exciton-bath coupling, which is not diagonal in either site excitation or exciton basis, results in a new inhomogeneous term that is absent in the expression for the absorption lineshape. Careful treatment of all the 2nd order terms are made, and explicit expressions are derived for both full 2nd order lineshape expression and the one based on secular approximation that neglects off-diagonal components in the exciton basis. Numerical results are presented for a few representative cases of disorder and temperature. Comparison of emission line shape with the absorption line shape is also made. It is shown that the inhomogeneous term coming from the entanglement of the system and bath degrees of freedom makes significant contributions to the lineshape. It is also found that the perturbative nature of the theory can result in negative portion of lineshape in some situations, which can be removed significantly by inclusion of the inhomogeneous term and completely by using the secular approximation. Comparison of the emission and absorption lineshapes at different temperatures demonstrates the role of thermal population of different exciton states and exciton phonon couplings.

View Accepted Manuscript (DOE)

Research Organization:: City Univ. of New York (CUNY), NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0001393

OSTI ID:: 1751947

Report Number(s):: DOE-Queens--1393-9

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 13 Vol. 138; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (59)

The Purple Phototrophic Bacteria Hunter, C. Neil; Daldal, Fevzi; Thurnauer, Marion C. Advances in Photosynthesis and Respiration, Vol. 28 https://doi.org/10.1007/978-1-4020-8815-5	book	September 2008
Origin and early evolution of photosynthesis Blankenship, Robert E. Photosynthesis Research, Vol. 33, Issue 2 https://doi.org/10.1007/BF00039173	journal	August 1992
Spectroscopy on the B850 Band of Individual Light-Harvesting 2 Complexes of Rhodopseudomonas acidophila I. Experiments and Monte Carlo Simulations Ketelaars, M.; van Oijen, A. M.; Matsushita, M. Biophysical Journal, Vol. 80, Issue 3 https://doi.org/10.1016/S0006-3495(01)76132-2	journal	March 2001
Spectroscopy on the B850 Band of Individual Light-Harvesting 2 Complexes of Rhodopseudomonas acidophila II. Exciton States of an Elliptically Deformed Ring Aggregate Matsushita, M.; Ketelaars, M.; van Oijen, A. M. Biophysical Journal, Vol. 80, Issue 3 https://doi.org/10.1016/S0006-3495(01)76133-4	journal	March 2001
Influence of static and dynamic disorder on the anisotropy of emission in the ring antenna subunits of purple bacteria photosynthetic systems Heřman, Pavel; Kleinekathöfer, Ulrich; Barvı́k, Ivan Chemical Physics, Vol. 275, Issue 1-3 https://doi.org/10.1016/S0301-0104(01)00520-1	journal	January 2002
Fluorescence depolarization dynamics in the B850 complex of purple bacteria Kühn, O.; Sundström, V.; Pullerits, T. Chemical Physics, Vol. 275, Issue 1-3 https://doi.org/10.1016/S0301-0104(01)00526-2	journal	January 2002
Ultrafast excitation energy transfer dynamics in photosynthetic pigment–protein complexes Renger, Thomas; May, Volkhard; Kühn, Oliver Physics Reports, Vol. 343, Issue 3 https://doi.org/10.1016/S0370-1573(00)00078-8	journal	March 2001
The mechanism of energy transfer in the antenna of photosynthetic purple bacteria Yang, Mino; Agarwal, Ritesh; Fleming, Graham R. Journal of Photochemistry and Photobiology A: Chemistry, Vol. 142, Issue 2-3 https://doi.org/10.1016/S1010-6030(01)00504-4	journal	September 2001
Fluorescence-emission spectroscopy of individual LH2 and LH3 complexes de Ruijter, W. P. F.; Segura, J. M.; Cogdell, R. J. Chemical Physics, Vol. 341, Issue 1-3 https://doi.org/10.1016/j.chemphys.2007.07.050	journal	November 2007
Two-dimensional electronic spectroscopy and photosynthesis: Fundamentals and applications to photosynthetic light-harvesting Schlau-Cohen, Gabriela S.; Ishizaki, Akihito; Fleming, Graham R. Chemical Physics, Vol. 386, Issue 1-3 https://doi.org/10.1016/j.chemphys.2011.04.025	journal	July 2011
Energetic disorder and the B850-exciton states of individual light-harvesting 2 complexes from Rhodopseudomonas acidophila Hofmann, Clemens; Aartsma, Thijs J.; Köhler, Jürgen Chemical Physics Letters, Vol. 395, Issue 4-6 https://doi.org/10.1016/j.cplett.2004.08.020	journal	September 2004
Non-Markovian effects in the anisotropy of fluorescence in LH2 units Schreiber, Michael; Heřman, Pavel; Barvı́k, Ivan Journal of Luminescence, Vol. 108, Issue 1-4 https://doi.org/10.1016/j.jlumin.2004.01.022	journal	June 2004
Protein dynamics revealed in the excitonic spectra of single LH2 complexes Valkunas, Leonas; Janusonis, Julius; Rutkauskas, Danielis Journal of Luminescence, Vol. 127, Issue 1 https://doi.org/10.1016/j.jlumin.2007.02.032	journal	November 2007
The Structure and Thermal Motion of the B800–850 LH2 Complex from Rps.acidophila at 2.0Å Resolution and 100K: New Structural Features and Functionally Relevant Motions Papiz, Miroslav Z.; Prince, Steve M.; Howard, Tina Journal of Molecular Biology, Vol. 326, Issue 5 https://doi.org/10.1016/s0022-2836(03)00024-X	journal	March 2003
Photosynthetic apparatus of purple bacteria Hu, Xiche; Ritz, Thorsten; Damjanović, Ana Quarterly Reviews of Biophysics, Vol. 35, Issue 1 https://doi.org/10.1017/S0033583501003754	journal	February 2002
The architecture and function of the light-harvesting apparatus of purple bacteria: from single molecules to in vivo membranes Cogdell, Richard J.; Gall, Andrew; Köhler, Jürgen Quarterly Reviews of Biophysics, Vol. 39, Issue 3 https://doi.org/10.1017/S0033583506004434	journal	August 2006
Fluorescence Spectral Fluctuations of Single LH2 Complexes from Rhodopseudomonas acidophila Strain 10050 ^† Rutkauskas, Danielis; Novoderezkhin, Vladimir; Cogdell, Richard J. Biochemistry, Vol. 43, Issue 15 https://doi.org/10.1021/bi0497648	journal	April 2004
Coherent Two-Dimensional Optical Spectroscopy Cho, Minhaeng Chemical Reviews, Vol. 108, Issue 4 https://doi.org/10.1021/cr078377b	journal	April 2008
Theoretical Study of Time-Resolved Fluorescence Anisotropy from Coupled Chromophore Pairs Matro, Alexander; Cina, Jeffrey A. The Journal of Physical Chemistry, Vol. 99, Issue 9 https://doi.org/10.1021/j100009a015	journal	March 1995
Energy Transfer Dynamics in LH2 Complexes of Rhodopseudomonas a cidophila Containing Only One B800 Molecule Matsuzaki, S.; Zazubovich, V.; Fraser, N. J. The Journal of Physical Chemistry B, Vol. 105, Issue 29 https://doi.org/10.1021/jp0037347	journal	July 2001
Characterization of the Static Disorder in the B850 Band of LH2 ^† Jang, Seogjoo; Dempster, Sara E.; Silbey, Robert J. The Journal of Physical Chemistry B, Vol. 105, Issue 28 https://doi.org/10.1021/jp010169e	journal	July 2001
Multichromophoric Förster Resonance Energy Transfer from B800 to B850 in the Light Harvesting Complex 2: Evidence for Subtle Energetic Optimization by Purple Bacteria ^† Jang, Seogjoo; Newton, Marshall D.; Silbey, Robert J. The Journal of Physical Chemistry B, Vol. 111, Issue 24 https://doi.org/10.1021/jp070111l	journal	June 2007
Is There Elliptic Distortion in the Light Harvesting Complex 2 of Purple Bacteria? Jang, Seogjoo; Silbey, Robert J.; Kunz, Ralf The Journal of Physical Chemistry B, Vol. 115, Issue 44 https://doi.org/10.1021/jp202344s	journal	November 2011
The Electronically Excited States of LH2 Complexes from Rhodopseudomonas acidophila Strain 10050 Studied by Time-Resolved Spectroscopy and Dynamic Monte Carlo Simulations. I. Isolated, Non-Interacting LH2 Complexes Pflock, Tobias J.; Oellerich, Silke; Southall, June The Journal of Physical Chemistry B, Vol. 115, Issue 28 https://doi.org/10.1021/jp202353c	journal	July 2011
Exciton Self Trapping in Photosynthetic Pigment–Protein Complexes Studied by Single-Molecule Spectroscopy Kunz, Ralf; Timpmann, Kõu; Southall, June The Journal of Physical Chemistry B, Vol. 116, Issue 36 https://doi.org/10.1021/jp3040456	journal	August 2012
Static and Dynamic Protein Impact on Electronic Properties of Light-Harvesting Complex LH2 Zerlauskiene, O.; Trinkunas, G.; Gall, A. The Journal of Physical Chemistry B, Vol. 112, Issue 49 https://doi.org/10.1021/jp803439w	journal	December 2008
Photosynthetic Light-Harvesting: Reconciling Dynamics and Structure of Purple Bacterial LH2 Reveals Function of Photosynthetic Unit Sundström, Villy; Pullerits, Tõnu; van Grondelle, Rienk The Journal of Physical Chemistry B, Vol. 103, Issue 13 https://doi.org/10.1021/jp983722+	journal	March 1999
How Quantum Coherence Assists Photosynthetic Light-Harvesting Strümpfer, J.; Şener, M.; Schulten, K. The Journal of Physical Chemistry Letters, Vol. 3, Issue 4 https://doi.org/10.1021/jz201459c	journal	January 2012
Crystal structure of an integral membrane light-harvesting complex from photosynthetic bacteria McDermott, G.; Prince, S. M.; Freer, A. A. Nature, Vol. 374, Issue 6522 https://doi.org/10.1038/374517a0	journal	April 1995
Quantum control of energy flow in light harvesting Herek, Jennifer L.; Wohlleben, Wendel; Cogdell, Richard J. Nature, Vol. 417, Issue 6888, p. 533-535 https://doi.org/10.1038/417533a	journal	May 2002
Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems Engel, Gregory S.; Calhoun, Tessa R.; Read, Elizabeth L. Nature, Vol. 446, Issue 7137 https://doi.org/10.1038/nature05678	journal	April 2007
Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature Collini, Elisabetta; Wong, Cathy Y.; Wilk, Krystyna E. Nature, Vol. 463, Issue 7281 https://doi.org/10.1038/nature08811	journal	February 2010
Four wave mixing spectroscopy for a multilevel system Sung, Jaeyoung; Silbey, Robert J. The Journal of Chemical Physics, Vol. 115, Issue 20 https://doi.org/10.1063/1.1413979	journal	November 2001
Theory of single molecule line shapes of multichromophoric macromolecules Jang, Seogjoo; Silbey, Robert J. The Journal of Chemical Physics, Vol. 118, Issue 20 https://doi.org/10.1063/1.1569239	journal	May 2003
Single complex line shapes of the B850 band of LH2 Jang, Seogjoo; Silbey, Robert J. The Journal of Chemical Physics, Vol. 118, Issue 20 https://doi.org/10.1063/1.1569240	journal	May 2003
Nonperturbative vibrational energy relaxation effects on vibrational line shapes Yang, Shilong; Shao, Jiushu; Cao, Jianshu The Journal of Chemical Physics, Vol. 121, Issue 22 https://doi.org/10.1063/1.1812748	journal	January 2004
Calculation of absorption spectra for light-harvesting systems using non-Markovian approaches as well as modified Redfield theory Schröder, Markus; Kleinekathöfer, Ulrich; Schreiber, Michael The Journal of Chemical Physics, Vol. 124, Issue 8 https://doi.org/10.1063/1.2171188	journal	February 2006
Optical line shapes of molecular aggregates: Hierarchical equations of motion method Chen, Liping; Zheng, Renhui; Shi, Qiang The Journal of Chemical Physics, Vol. 131, Issue 9 https://doi.org/10.1063/1.3213013	journal	January 2009
Light harvesting complex II B850 excitation dynamics Strümpfer, Johan; Schulten, Klaus The Journal of Chemical Physics, Vol. 131, Issue 22 https://doi.org/10.1063/1.3271348	journal	December 2009
Iterative linearized density matrix propagation for modeling coherent excitation energy transfer in photosynthetic light harvesting Huo, P.; Coker, D. F. The Journal of Chemical Physics, Vol. 133, Issue 18 https://doi.org/10.1063/1.3498901	journal	November 2010
The effect of correlated bath fluctuations on exciton transfer Strümpfer, Johan; Schulten, Klaus The Journal of Chemical Physics, Vol. 134, Issue 9 https://doi.org/10.1063/1.3557042	journal	March 2011
Controlling the efficiency of an artificial light-harvesting complex Savolainen, J.; Fanciulli, R.; Dijkhuizen, N. Proceedings of the National Academy of Sciences, Vol. 105, Issue 22 https://doi.org/10.1073/pnas.0711927105	journal	May 2008
Quantum coherence spectroscopy reveals complex dynamics in bacterial light-harvesting complex 2 (LH2) Harel, E.; Engel, G. S. Proceedings of the National Academy of Sciences, Vol. 109, Issue 3 https://doi.org/10.1073/pnas.1110312109	journal	January 2012
Direct observation of tiers in the energy landscape of a chromoprotein: A single-molecule study Hofmann, C.; Aartsma, T. J.; Michel, H. Proceedings of the National Academy of Sciences, Vol. 100, Issue 26 https://doi.org/10.1073/pnas.2533896100	journal	December 2003
Fluorescence and photobleaching dynamics of single light-harvesting complexes Bopp, M. A.; Jia, Y.; Li, L. Proceedings of the National Academy of Sciences, Vol. 94, Issue 20 https://doi.org/10.1073/pnas.94.20.10630	journal	September 1997
The dynamics of structural deformations of immobilized single light-harvesting complexes Bopp, M. A.; Sytnik, A.; Howard, T. D. Proceedings of the National Academy of Sciences, Vol. 96, Issue 20 https://doi.org/10.1073/pnas.96.20.11271	journal	September 1999
Equilibrium-reduced density matrix formulation: Influence of noise, disorder, and temperature on localization in excitonic systems Moix, Jeremy M.; Zhao, Yang; Cao, Jianshu Physical Review B, Vol. 85, Issue 11 https://doi.org/10.1103/PhysRevB.85.115412	journal	March 2012
Excitons in a photosynthetic light-harvesting system: A combined molecular dynamics, quantum chemistry, and polaron model study Damjanović, Ana; Kosztin, Ioan; Kleinekathöfer, Ulrich Physical Review E, Vol. 65, Issue 3 https://doi.org/10.1103/PhysRevE.65.031919	journal	March 2002
Multiple Exciton Effects in Molecular Aggregates: Application to a Photosynthetic Antenna Complex Renger, Thomas; May, Volkhard Physical Review Letters, Vol. 78, Issue 17 https://doi.org/10.1103/PhysRevLett.78.3406	journal	April 1997
Multichromophoric Förster Resonance Energy Transfer Jang, Seogjoo; Newton, Marshall D.; Silbey, Robert J. Physical Review Letters, Vol. 92, Issue 21 https://doi.org/10.1103/PhysRevLett.92.218301	journal	May 2004
Coherence in the B800 Ring of Purple Bacteria LH2 Cheng, Y. C.; Silbey, R. J. Physical Review Letters, Vol. 96, Issue 2 https://doi.org/10.1103/PhysRevLett.96.028103	journal	January 2006
Early Evolution of Photosynthesis Blankenship, Robert E. Plant Physiology, Vol. 154, Issue 2 https://doi.org/10.1104/pp.110.161687	journal	October 2010
Unraveling the Electronic Structure of Individual Photosynthetic Pigment-Protein Complexes van Oijen, A. M. Science, Vol. 285, Issue 5426 https://doi.org/10.1126/science.285.5426.400	journal	July 1999
T WO -D IMENSIONAL F EMTOSECOND S PECTROSCOPY Jonas, David M. Annual Review of Physical Chemistry, Vol. 54, Issue 1 https://doi.org/10.1146/annurev.physchem.54.011002.103907	journal	October 2003
RETRACTED: Fluorescence Spectroscopy of Conformational Changes of Single LH2 Complexes Rutkauskas, Danielis; Novoderezhkin, Vladimir; Cogdell, Richard J. Biophysical Journal, Vol. 88, Issue 1 https://doi.org/10.1529/biophysj.104.048629	journal	January 2005
Dynamics of the Emission Spectrum of a Single LH2 Complex: Interplay of Slow and Fast Nuclear Motions Novoderezhkin, Vladimir I.; Rutkauskas, Danielis; van Grondelle, Rienk Biophysical Journal, Vol. 90, Issue 8 https://doi.org/10.1529/biophysj.105.072652	journal	April 2006
Spectral Trends in the Fluorescence of Single Bacterial Light-Harvesting Complexes: Experiments and Modified Redfield Simulations Rutkauskas, Danielis; Novoderezhkin, Vladimir; Gall, Andrew Biophysical Journal, Vol. 90, Issue 7 https://doi.org/10.1529/biophysj.105.075903	journal	April 2006
Spectral Dynamics of Individual Bacterial Light-Harvesting Complexes: Alternative Disorder Model Janusonis, Julius; Valkunas, Leonas; Rutkauskas, Danielis Biophysical Journal, Vol. 94, Issue 4 https://doi.org/10.1529/biophysj.107.108431	journal	February 2008
Multistep Quantum Master Equation Theory for Response Functions in Four Wave Mixing Electronic Spectroscopy of Multichromophoric Macromolecules Jang, Seog-Joo Bulletin of the Korean Chemical Society, Vol. 33, Issue 3 https://doi.org/10.5012/bkcs.2012.33.3.997	journal	March 2012

Cited By (4)

Fourth order expressions for the electronic absorption lineshape of molecular excitons Jang, Seogjoo J. The Journal of Chemical Physics, Vol. 151, Issue 4 https://doi.org/10.1063/1.5100986	journal	July 2019
Analytical derivation of equilibrium state for open quantum system Gelzinis, Andrius; Valkunas, Leonas The Journal of Chemical Physics, Vol. 152, Issue 5 https://doi.org/10.1063/1.5141519	journal	February 2020
Delocalized excitons in natural light-harvesting complexes Jang, Seogjoo J.; Mennucci, Benedetta Reviews of Modern Physics, Vol. 90, Issue 3 https://doi.org/10.1103/revmodphys.90.035003	journal	August 2018
Delocalized excitons in natural light harvesting complexes Jang, Seogjoo J.; Mennucci, Benedetta arXiv https://doi.org/10.48550/arxiv.1804.09711	text	January 2018

Similar Records

Fourth order expressions for the electronic absorption lineshape of molecular excitons

Journal Article · Sun Jul 28 20:00:00 EDT 2019 · Journal of Chemical Physics · OSTI ID:1610558

Multistep Quantum Master Equation Theory for Response Functions in Four Wave Mixing Electronic Spectroscopy of Multichromophoric Macromolecules

Journal Article · Mon Mar 19 20:00:00 EDT 2012 · Bulletin of the Korean Chemical Society · OSTI ID:1751910

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Absorption line
Bacteria
Complex analysis
Emission Lineshape
Excitation energies
Excitons
Light harvesting complex 2
Light harvesting complexes
Oscillator strengths
Phonons
Purple bacteria
Quantum chemical dynamics
Quantum master equation
Stochastic processes

Emission lineshapes of the B850 band of light-harvesting 2 (LH2) complex in purple bacteria: A second order time-nonlocal quantum master equation approach

Citation Formats

References (59)

Cited By (4)

Similar Records

Related Subjects