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Title: Strongly coupled bacteriochlorin dyad studied using phase-modulated fluorescence-detected two-dimensional electronic spectroscopy

Abstract

Fluorescence-detected two-dimensional electronic spectroscopy (F-2DES) projects the third-order non-linear polarization in a system as an excited electronic state population which is incoherently detected as fluorescence. Multiple variants of F-2DES have been developed. Here, we report phase-modulated F-2DES measurements on a strongly coupled symmetric bacteriochlorin dyad, a relevant ‘toy’ model for photosynthetic energy and charge transfer. Coherence map analysis shows that the strongest frequency observed in the dyad is well-separated from the excited state electronic energy gap, and is consistent with a vibrational frequency readily observed in bacteriochlorin monomers. Kinetic rate maps show a picosecond relaxation timescale between the excited states of the dyad. To our knowledge this is the first demonstration of coherence and kinetic analysis using the phase-modulation approach to F-2DES.

Authors:
ORCiD logo; ; ORCiD logo; ; ; ; ; ;
Publication Date:
Research Org.:
Washington Univ., St. Louis, MO (United States); Univ. of Michigan, Ann Arbor, MI (United States); Univ. of Maryland Baltimore County (UMBC), Baltimore, MD (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); US Air Force Office of Scientific Research (AFOSR); National Science Foundation (NSF)
OSTI Identifier:
1464591
Alternate Identifier(s):
OSTI ID: 1502496
Grant/Contract Number:  
FG02-05ER15661; FA9550-15-1-0210; CHE-1301109
Resource Type:
Published Article
Journal Name:
Optics Express
Additional Journal Information:
Journal Name: Optics Express Journal Volume: 26 Journal Issue: 17; Journal ID: ISSN 1094-4087
Publisher:
Optical Society of America
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; absorption spectroscopy; electric fields; energy transfer; light matter interactions; phase modulation; spatial light modulators

Citation Formats

Tiwari, Vivek, Matutes, Yassel Acosta, Konar, Arkaprabha, Yu, Zhanqian, Ptaszek, Marcin, Bocian, David F., Holten, Dewey, Kirmaier, Christine, and Ogilvie, Jennifer P. Strongly coupled bacteriochlorin dyad studied using phase-modulated fluorescence-detected two-dimensional electronic spectroscopy. United States: N. p., 2018. Web. doi:10.1364/OE.26.022327.
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Tiwari, Vivek, Matutes, Yassel Acosta, Konar, Arkaprabha, Yu, Zhanqian, Ptaszek, Marcin, Bocian, David F., Holten, Dewey, Kirmaier, Christine, & Ogilvie, Jennifer P. Strongly coupled bacteriochlorin dyad studied using phase-modulated fluorescence-detected two-dimensional electronic spectroscopy. United States. https://doi.org/10.1364/OE.26.022327
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Tiwari, Vivek, Matutes, Yassel Acosta, Konar, Arkaprabha, Yu, Zhanqian, Ptaszek, Marcin, Bocian, David F., Holten, Dewey, Kirmaier, Christine, and Ogilvie, Jennifer P. Tue . "Strongly coupled bacteriochlorin dyad studied using phase-modulated fluorescence-detected two-dimensional electronic spectroscopy". United States. https://doi.org/10.1364/OE.26.022327.
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@article{osti_1464591,
title = {Strongly coupled bacteriochlorin dyad studied using phase-modulated fluorescence-detected two-dimensional electronic spectroscopy},
author = {Tiwari, Vivek and Matutes, Yassel Acosta and Konar, Arkaprabha and Yu, Zhanqian and Ptaszek, Marcin and Bocian, David F. and Holten, Dewey and Kirmaier, Christine and Ogilvie, Jennifer P.},
abstractNote = {Fluorescence-detected two-dimensional electronic spectroscopy (F-2DES) projects the third-order non-linear polarization in a system as an excited electronic state population which is incoherently detected as fluorescence. Multiple variants of F-2DES have been developed. Here, we report phase-modulated F-2DES measurements on a strongly coupled symmetric bacteriochlorin dyad, a relevant ‘toy’ model for photosynthetic energy and charge transfer. Coherence map analysis shows that the strongest frequency observed in the dyad is well-separated from the excited state electronic energy gap, and is consistent with a vibrational frequency readily observed in bacteriochlorin monomers. Kinetic rate maps show a picosecond relaxation timescale between the excited states of the dyad. To our knowledge this is the first demonstration of coherence and kinetic analysis using the phase-modulation approach to F-2DES.},
doi = {10.1364/OE.26.022327},
journal = {Optics Express},
number = 17,
volume = 26,
place = {United States},
year = {Tue Aug 14 00:00:00 EDT 2018},
month = {Tue Aug 14 00:00:00 EDT 2018}
}
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https://doi.org/10.1364/OE.26.022327
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