The nature of singlet excitons in oligoacene molecular crystals

Handle URI:
http://hdl.handle.net/10754/599941
Title:
The nature of singlet excitons in oligoacene molecular crystals
Authors:
Yamagata, H.; Norton, J.; Hontz, E.; Olivier, Y.; Beljonne, D.; Brédas, J. L.; Silbey, R. J.; Spano, F. C.
Abstract:
A theory for polarized absorption in crystalline oligoacenes is presented, which includes Frenkel exciton coupling, the coupling between Frenkel and charge-transfer (CT) excitons, and the coupling of all neutral and ionic excited states to the dominant ring-breathing vibrational mode. For tetracene, spectra calculated using all Frenkel couplings among the five lowest energy molecular singlet states predict a Davydov splitting (DS) of the lowest energy (0-0) vibronic band of only -32cm-1, far smaller than the measured value of 631cm-1 and of the wrong sign-a negative sign indicating that the polarizations of the lower and upper Davydov components are reversed from experiment. Inclusion of Frenkel-CT coupling dramatically improves the agreement with experiment, yielding a 0-0 DS of 601cm-1 and a nearly quantitative reproduction of the relative spectral intensities of the 0-n vibronic components. Our analysis also shows that CT mixing increases with the size of the oligoacenes. We discuss the implications of these results on exciton dissociation and transport. © 2011 American Institute of Physics.
Citation:
Yamagata H, Norton J, Hontz E, Olivier Y, Beljonne D, et al. (2011) The nature of singlet excitons in oligoacene molecular crystals. J Chem Phys 134: 204703. Available: http://dx.doi.org/10.1063/1.3590871.
Publisher:
AIP Publishing
Journal:
The Journal of Chemical Physics
KAUST Grant Number:
KUSC1-015-21
Issue Date:
2011
DOI:
10.1063/1.3590871
PubMed ID:
21639463
Type:
Article
ISSN:
0021-9606
Sponsors:
F.C.S. and H.Y. were supported by the National Science Foundation (NSF) under Award DMR-0906464. Work at Georgia Tech was partly supported by the Office of Naval Research (ONR), the STC Program of the National Science Foundation under Award DMR-0120967, and the Center for Advanced Molecular Photovoltaics, Award No KUSC1-015-21, made by King Abdullah University of Science and Technology (KAUST). Research in University of Mons was supported by the Interuniversity Attraction Pole program of the Belgian Federal Science Policy Office (PAI 6/27), Programme d'Excellence de la Region Wallonne (OPTI2MAT project), and FNRS-FRFC; D. B. is an FNRS Research Director. R.J.S. was supported as part of the Center for Excitonics, an Energy Frontier Research Center funded by U.S. Department of Energy and Office of Science, Office of Basic Energy Science (Grant No. DE-SC0001088).
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Full metadata record

DC FieldValue Language
dc.contributor.authorYamagata, H.en
dc.contributor.authorNorton, J.en
dc.contributor.authorHontz, E.en
dc.contributor.authorOlivier, Y.en
dc.contributor.authorBeljonne, D.en
dc.contributor.authorBrédas, J. L.en
dc.contributor.authorSilbey, R. J.en
dc.contributor.authorSpano, F. C.en
dc.date.accessioned2016-02-28T06:32:55Zen
dc.date.available2016-02-28T06:32:55Zen
dc.date.issued2011en
dc.identifier.citationYamagata H, Norton J, Hontz E, Olivier Y, Beljonne D, et al. (2011) The nature of singlet excitons in oligoacene molecular crystals. J Chem Phys 134: 204703. Available: http://dx.doi.org/10.1063/1.3590871.en
dc.identifier.issn0021-9606en
dc.identifier.pmid21639463en
dc.identifier.doi10.1063/1.3590871en
dc.identifier.urihttp://hdl.handle.net/10754/599941en
dc.description.abstractA theory for polarized absorption in crystalline oligoacenes is presented, which includes Frenkel exciton coupling, the coupling between Frenkel and charge-transfer (CT) excitons, and the coupling of all neutral and ionic excited states to the dominant ring-breathing vibrational mode. For tetracene, spectra calculated using all Frenkel couplings among the five lowest energy molecular singlet states predict a Davydov splitting (DS) of the lowest energy (0-0) vibronic band of only -32cm-1, far smaller than the measured value of 631cm-1 and of the wrong sign-a negative sign indicating that the polarizations of the lower and upper Davydov components are reversed from experiment. Inclusion of Frenkel-CT coupling dramatically improves the agreement with experiment, yielding a 0-0 DS of 601cm-1 and a nearly quantitative reproduction of the relative spectral intensities of the 0-n vibronic components. Our analysis also shows that CT mixing increases with the size of the oligoacenes. We discuss the implications of these results on exciton dissociation and transport. © 2011 American Institute of Physics.en
dc.description.sponsorshipF.C.S. and H.Y. were supported by the National Science Foundation (NSF) under Award DMR-0906464. Work at Georgia Tech was partly supported by the Office of Naval Research (ONR), the STC Program of the National Science Foundation under Award DMR-0120967, and the Center for Advanced Molecular Photovoltaics, Award No KUSC1-015-21, made by King Abdullah University of Science and Technology (KAUST). Research in University of Mons was supported by the Interuniversity Attraction Pole program of the Belgian Federal Science Policy Office (PAI 6/27), Programme d'Excellence de la Region Wallonne (OPTI2MAT project), and FNRS-FRFC; D. B. is an FNRS Research Director. R.J.S. was supported as part of the Center for Excitonics, an Energy Frontier Research Center funded by U.S. Department of Energy and Office of Science, Office of Basic Energy Science (Grant No. DE-SC0001088).en
dc.publisherAIP Publishingen
dc.titleThe nature of singlet excitons in oligoacene molecular crystalsen
dc.typeArticleen
dc.identifier.journalThe Journal of Chemical Physicsen
dc.contributor.institutionTemple University, Philadelphia, United Statesen
dc.contributor.institutionGeorgia Institute of Technology, Atlanta, United Statesen
dc.contributor.institutionUniversité de Mons, Mons, Belgiumen
dc.contributor.institutionMassachusetts Institute of Technology, Cambridge, United Statesen
kaust.grant.numberKUSC1-015-21en
kaust.grant.fundedcenterCenter for Advanced Molecular Photovoltaics (CAMP)en

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