The separation of vibrational coherence from ground- and excited-electronic states in P3HT film

Handle URI:
http://hdl.handle.net/10754/599962
Title:
The separation of vibrational coherence from ground- and excited-electronic states in P3HT film
Authors:
Song, Yin; Hellmann, Christoph; Stingelin, Natalie; Scholes, Gregory D.
Abstract:
© 2015 AIP Publishing LLC. Concurrence of the vibrational coherence and ultrafast electron transfer has been observed in polymer/fullerene blends. However, it is difficult to experimentally investigate the role that the excited-state vibrational coherence plays during the electron transfer process since vibrational coherence from the ground- and excited-electronic states is usually temporally and spectrally overlapped. Here, we performed 2-dimensional electronic spectroscopy (2D ES) measurements on poly(3-hexylthiophene) (P3HT) films. By Fourier transforming the whole 2D ES datasets (S (λ 1, T∼ 2, λ 3)) along the population time (T∼ 2) axis, we develop and propose a protocol capable of separating vibrational coherence from the ground- and excited-electronic states in 3D rephasing and nonrephasing beating maps (S (λ 1, ν∼ 2, λ 3)). We found that the vibrational coherence from pure excited electronic states appears at positive frequency (+ ν∼ 2) in the rephasing beating map and at negative frequency (- ν∼ 2) in the nonrephasing beating map. Furthermore, we also found that vibrational coherence from excited electronic state had a long dephasing time of 244 fs. The long-lived excited-state vibrational coherence indicates that coherence may be involved in the electron transfer process. Our findings not only shed light on the mechanism of ultrafast electron transfer in organic photovoltaics but also are beneficial for the study of the coherence effect on photoexcited dynamics in other systems.
Citation:
Song Y, Hellmann C, Stingelin N, Scholes GD (2015) The separation of vibrational coherence from ground- and excited-electronic states in P3HT film. J Chem Phys 142: 212410. Available: http://dx.doi.org/10.1063/1.4916325.
Publisher:
AIP Publishing
Journal:
The Journal of Chemical Physics
Issue Date:
7-Jun-2015
DOI:
10.1063/1.4916325
PubMed ID:
26049430
Type:
Article
ISSN:
0021-9606; 1089-7690
Sponsors:
G.D.S. acknowledges financial support for this work from the Natural Sciences and Engineering Research Council of Canada (through NSERC Polanyi Award). Y.S. would like to thank Dr. Ryan D. Pensack for stimulating discussion. C.H. was supported by a KAUST Global Collaborative Research Academic Excellence Alliance (AEA) grant.
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Full metadata record

DC FieldValue Language
dc.contributor.authorSong, Yinen
dc.contributor.authorHellmann, Christophen
dc.contributor.authorStingelin, Natalieen
dc.contributor.authorScholes, Gregory D.en
dc.date.accessioned2016-02-28T06:33:21Zen
dc.date.available2016-02-28T06:33:21Zen
dc.date.issued2015-06-07en
dc.identifier.citationSong Y, Hellmann C, Stingelin N, Scholes GD (2015) The separation of vibrational coherence from ground- and excited-electronic states in P3HT film. J Chem Phys 142: 212410. Available: http://dx.doi.org/10.1063/1.4916325.en
dc.identifier.issn0021-9606en
dc.identifier.issn1089-7690en
dc.identifier.pmid26049430en
dc.identifier.doi10.1063/1.4916325en
dc.identifier.urihttp://hdl.handle.net/10754/599962en
dc.description.abstract© 2015 AIP Publishing LLC. Concurrence of the vibrational coherence and ultrafast electron transfer has been observed in polymer/fullerene blends. However, it is difficult to experimentally investigate the role that the excited-state vibrational coherence plays during the electron transfer process since vibrational coherence from the ground- and excited-electronic states is usually temporally and spectrally overlapped. Here, we performed 2-dimensional electronic spectroscopy (2D ES) measurements on poly(3-hexylthiophene) (P3HT) films. By Fourier transforming the whole 2D ES datasets (S (λ 1, T∼ 2, λ 3)) along the population time (T∼ 2) axis, we develop and propose a protocol capable of separating vibrational coherence from the ground- and excited-electronic states in 3D rephasing and nonrephasing beating maps (S (λ 1, ν∼ 2, λ 3)). We found that the vibrational coherence from pure excited electronic states appears at positive frequency (+ ν∼ 2) in the rephasing beating map and at negative frequency (- ν∼ 2) in the nonrephasing beating map. Furthermore, we also found that vibrational coherence from excited electronic state had a long dephasing time of 244 fs. The long-lived excited-state vibrational coherence indicates that coherence may be involved in the electron transfer process. Our findings not only shed light on the mechanism of ultrafast electron transfer in organic photovoltaics but also are beneficial for the study of the coherence effect on photoexcited dynamics in other systems.en
dc.description.sponsorshipG.D.S. acknowledges financial support for this work from the Natural Sciences and Engineering Research Council of Canada (through NSERC Polanyi Award). Y.S. would like to thank Dr. Ryan D. Pensack for stimulating discussion. C.H. was supported by a KAUST Global Collaborative Research Academic Excellence Alliance (AEA) grant.en
dc.publisherAIP Publishingen
dc.titleThe separation of vibrational coherence from ground- and excited-electronic states in P3HT filmen
dc.typeArticleen
dc.identifier.journalThe Journal of Chemical Physicsen
dc.contributor.institutionDepartment of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6, Canadaen
dc.contributor.institutionDepartment of Materials and Centre for Plastic Electronics, Imperial College London, South Kensington Campus, London SW7 2AZ, United Kingdomen
dc.contributor.institutionDepartment of Chemistry, Princeton University, Washington Road, Princeton, New Jersey 08544, USAen
kaust.grant.programAcademic Excellence Alliance (AEA)en
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