Two-Dimensional Electronic-Vibrational Spectroscopy of Chlorophyll a and b

Lewis, Nicholas H.  C.; Fleming, Graham R.

doi:10.1021/acs.jpclett.6b00037

Title: Two-Dimensional Electronic-Vibrational Spectroscopy of Chlorophyll a and b

Journal Article · Thu Mar 03 00:00:00 EST 2016 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.6b00037· OSTI ID:1379232

Lewis, Nicholas H. C. ^[1]; Fleming, Graham R. ^[1]

Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Div.; Kavli Energy Nanoscience Institute at Berkeley, CA (United States)

Presented are two-dimensional electronic-vibrational (2DEV) spectra of isolated chlorophyll a and b in deuterated ethanol. We excite the Q-band electronic transitions and measure the effects on the carbonyl and C=C double-bond stretch region of the infrared spectrum. With the aid of density functional theory calculations, we provide assignments for the major features of the spectrum. We show how the 2DEV spectra can be used to readily distinguish different solvation states of the chlorophyll, with features corresponding to the minority pentacoordinate magnesium (Mg) species being resolved along each dimension of the 2DEV spectra from the dominant hexacoordinate Mg species. These assignments represent a crucial first step toward the application of 2DEV spectroscopy to chlorophyll-containing pigment-protein complexes.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1379232

Journal Information:: Journal of Physical Chemistry Letters, Vol. 7, Issue 5; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 45 works

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References (30)

Molecular Mechanisms of Photosynthesis Blankenship, Robert E. https://doi.org/10.1002/9780470758472	book	December 2002
Quantum Coherence Enabled Determination of the Energy Landscape in Light-Harvesting Complex II Calhoun, Tessa R.; Ginsberg, Naomi S.; Schlau-Cohen, Gabriela S. The Journal of Physical Chemistry B, Vol. 113, Issue 51 https://doi.org/10.1021/jp908300c	journal	December 2009
Pathways of Energy Flow in LHCII from Two-Dimensional Electronic Spectroscopy Schlau-Cohen, Gabriela S.; Calhoun, Tessa R.; Ginsberg, Naomi S. The Journal of Physical Chemistry B, Vol. 113, Issue 46 https://doi.org/10.1021/jp9066586	journal	November 2009
Spectroscopic elucidation of uncoupled transition energies in the major photosynthetic light-harvesting complex, LHCII Schlau-Cohen, G. S.; Calhoun, T. R.; Ginsberg, N. S. Proceedings of the National Academy of Sciences, Vol. 107, Issue 30 https://doi.org/10.1073/pnas.1006230107	journal	July 2010
Extracting the Excitonic Hamiltonian of the Fenna-Matthews-Olson Complex Using Three-Dimensional Third-Order Electronic Spectroscopy Hayes, Dugan; Engel, Gregory S. Biophysical Journal, Vol. 100, Issue 8 https://doi.org/10.1016/j.bpj.2010.12.3747	journal	April 2011
Two-Dimensional Electronic Spectroscopy Reveals Ultrafast Downhill Energy Transfer in Photosystem I Trimers of the Cyanobacterium Thermosynechococcus elongatus Anna, Jessica M.; Ostroumov, Evgeny E.; Maghlaoui, Karim The Journal of Physical Chemistry Letters, Vol. 3, Issue 24 https://doi.org/10.1021/jz3018013	journal	November 2012
Energy Transfer Pathways in Light-Harvesting Complexes of Purple Bacteria as Revealed by Global Kinetic Analysis of Two-Dimensional Transient Spectra Ostroumov, Evgeny E.; Mulvaney, Rachel M.; Anna, Jessica M. The Journal of Physical Chemistry B, Vol. 117, Issue 38 https://doi.org/10.1021/jp403028x	journal	April 2013
Probing energy transfer events in the light harvesting complex 2 (LH2) of Rhodobacter sphaeroides with two-dimensional spectroscopy Fidler, Andrew F.; Singh, Ved P.; Long, Phillip D. The Journal of Chemical Physics, Vol. 139, Issue 15 https://doi.org/10.1063/1.4824637	journal	October 2013
2D Electronic Spectroscopy Reveals Excitonic Structure in the Baseplate of a Chlorosome Dostál, Jakub; Vácha, František; Pšenčík, Jakub The Journal of Physical Chemistry Letters, Vol. 5, Issue 10 https://doi.org/10.1021/jz5005279	journal	May 2014
Coherence and population dynamics of chlorophyll excitations in FCP complex: Two-dimensional spectroscopy study Butkus, Vytautas; Gelzinis, Andrius; Augulis, Ramūnas The Journal of Chemical Physics, Vol. 142, Issue 21 https://doi.org/10.1063/1.4914098	journal	April 2015
Two-Dimensional Electronic Spectroscopy of Light-Harvesting Complex II at Ambient Temperature: A Joint Experimental and Theoretical Study Duan, Hong-Guang; Stevens, Amy L.; Nalbach, Peter The Journal of Physical Chemistry B, Vol. 119, Issue 36 https://doi.org/10.1021/acs.jpcb.5b05592	journal	August 2015
A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy Lewis, Nicholas H. C.; Dong, Hui; Oliver, Thomas A. A. The Journal of Chemical Physics, Vol. 143, Issue 12 https://doi.org/10.1063/1.4931634	journal	September 2015
Correlating the motion of electrons and nuclei with two-dimensional electronic-vibrational spectroscopy Oliver, T. A. A.; Lewis, N. H. C.; Fleming, G. R. Proceedings of the National Academy of Sciences, Vol. 111, Issue 28 https://doi.org/10.1073/pnas.1409207111	journal	June 2014
Determining the static electronic and vibrational energy correlations via two-dimensional electronic-vibrational spectroscopy Dong, Hui; Lewis, Nicholas H. C.; Oliver, Thomas A. A. The Journal of Chemical Physics, Vol. 142, Issue 17 https://doi.org/10.1063/1.4919684	journal	May 2015
Measuring correlated electronic and vibrational spectral dynamics using line shapes in two-dimensional electronic-vibrational spectroscopy Lewis, Nicholas H. C.; Dong, Hui; Oliver, Thomas A. A. The Journal of Chemical Physics, Vol. 142, Issue 17 https://doi.org/10.1063/1.4919686	journal	May 2015
Principles of Fluorescence Spectroscopy Lakowicz, Joseph R. Springer New York, NY https://doi.org/10.1007/978-0-387-46312-4	book	January 2006
Pump−Probe Polarization Anisotropy Study of Femtosecond Energy Transfer within the Photosynthetic Reaction Center of Rhodobacter sphaeroides R26 Jonas, David M.; Lang, Matthew J.; Nagasawa, Yutaka The Journal of Physical Chemistry, Vol. 100, Issue 30 https://doi.org/10.1021/jp960708t	journal	January 1996
On the calculation of rotational anisotropy decay, as measured by ultrafast polarization-resolved vibrational pump-probe experiments Lin, Y. -S.; Pieniazek, P. A.; Yang, Mino The Journal of Chemical Physics, Vol. 132, Issue 17 https://doi.org/10.1063/1.3409561	journal	May 2010
Surface-enhanced resonance Raman spectroscopy of copper chlorophyllin on silver and gold colloids Hildebrandt, Peter; Spiro, Thomas G. The Journal of Physical Chemistry, Vol. 92, Issue 12 https://doi.org/10.1021/j100323a010	journal	June 1988
Normal-mode characteristics of chlorophyll models. Vibrational analysis of metallooctaethylchlorins and their selectively deuterated analogs Fonda, Harold N.; Oertling, W. Anthony; Salehi, Asaad Journal of the American Chemical Society, Vol. 112, Issue 26 https://doi.org/10.1021/ja00182a008	journal	December 1990
Measurement of the Fluorescence Lifetime of Chlorophyll a In Vivo Singhal, G. S.; Rabinowitch, E. Biophysical Journal, Vol. 9, Issue 4 https://doi.org/10.1016/S0006-3495(69)86405-2	journal	April 1969
Molecular orientational relaxation times in liquids Mourou, G.; Malley, M. M. Optics Communications, Vol. 13, Issue 4 https://doi.org/10.1016/0030-4018(75)90135-2	journal	April 1975
Assignment of the Q-Bands of the Chlorophylls: Coherence Loss via Qx − Qy Mixing Reimers, Jeffrey R.; Cai, Zheng-Li; Kobayashi, Rika Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep02761	journal	September 2013
Non-radiative relaxation of photoexcited chlorophylls: theoretical and experimental study Bricker, William P.; Shenai, Prathamesh M.; Ghosh, Avishek Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep13625	journal	September 2015
Characterization of bacteriochlorophyll interactions in vitro by resonance Raman spectroscopy Cotton, Therese M.; Van Duyne, Richard P. Journal of the American Chemical Society, Vol. 103, Issue 20 https://doi.org/10.1021/ja00410a005	journal	October 1981
Resonance Raman and infrared studies on axial coordination to chlorophylls a and b in vitro Fujiwara, Masao; Tasumi, Mitsuo The Journal of Physical Chemistry, Vol. 90, Issue 2 https://doi.org/10.1021/j100274a009	journal	January 1986
State of chlorophyll a in vitro and in vivo from electronic transition spectra, and the nature of antenna chlorophyll Cotton, T. M.; Trifunac, A. D.; Ballschmiter, K. Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 368, Issue 2 https://doi.org/10.1016/0005-2728(74)90148-0	journal	November 1974
Evidence for 5- and 6-coordinated magnesium in bacteriochlorophyll a from visible absorption spectroscopy Evans, Thomas A.; Katz, Joseph J. Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 396, Issue 3 https://doi.org/10.1016/0005-2728(75)90147-4	journal	September 1975
Hydrogen-bond lifetime measured by time-resolved 2D-IR spectroscopy: N-methylacetamide in methanol Woutersen, S.; Mu, Y.; Stock, G. Chemical Physics, Vol. 266, Issue 2-3 https://doi.org/10.1016/S0301-0104(01)00224-5	journal	May 2001
Ultrafast Dynamics of Solute-Solvent Complexation Observed at Thermal Equilibrium in Real Time Zheng, J. Science, Vol. 309, Issue 5739 https://doi.org/10.1126/science.1116213	journal	August 2005

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