Charge Delocalization in Oligomers of Poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene), PBTTT

Handle URI:
http://hdl.handle.net/10754/608239
Title:
Charge Delocalization in Oligomers of Poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene), PBTTT
Authors:
Zhang, Yuexing; Steyrleuthner, Robert; Bredas, Jean-Luc ( 0000-0001-7278-4471 )
Abstract:
We investigate theoretically charge delocalization in radical-cations, i.e., positive polarons, formed on oligomer chains of poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene), PBTTT. We use non-empirically tuned range-separated density functionals (TRS-DFT), including LC-ωPBE, LC-BLYP, and ωB97XD. We consider the evolution with oligomer length of the molecular geometric and electronic structures, optical absorption features, and spin densities. The TRS-DFT results indicate that a positive polaron can delocalize ideally over some 10 thiophene rings when the backbone is non-planar and up to 14 rings for a backbone forced to be completely planar. Interestingly, up to six polarons can co-exist side-by-side in a hexamer (which contains 24 thiophene rings), which is consistent with the highest degrees of doping (oxidation) experimentally achievable in polythiophene derivatives.
KAUST Department:
Solar and Photovoltaic Engineering Research Center (SPERC)
Citation:
Charge Delocalization in Oligomers of Poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene), PBTTT 2016 The Journal of Physical Chemistry C
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Physical Chemistry C
Issue Date:
25-Apr-2016
DOI:
10.1021/acs.jpcc.6b02378
Type:
Article
ISSN:
1932-7447; 1932-7455
Sponsors:
This work has been supported by King Abdullah University of Science and Technology (KAUST). We acknowledge the KAUST IT Research Computing Team for providing computational and storage resources and thank Dr. Cheng Zhong, Dr. Haitao Sun, and Dr. Bradley D. Rose for stimulating discussions.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.6b02378
Appears in Collections:
Articles; Solar and Photovoltaic Engineering Research Center (SPERC)

Full metadata record

DC FieldValue Language
dc.contributor.authorZhang, Yuexingen
dc.contributor.authorSteyrleuthner, Roberten
dc.contributor.authorBredas, Jean-Lucen
dc.date.accessioned2016-05-04T13:58:32Zen
dc.date.available2016-05-04T13:58:32Zen
dc.date.issued2016-04-25en
dc.identifier.citationCharge Delocalization in Oligomers of Poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene), PBTTT 2016 The Journal of Physical Chemistry Cen
dc.identifier.issn1932-7447en
dc.identifier.issn1932-7455en
dc.identifier.doi10.1021/acs.jpcc.6b02378en
dc.identifier.urihttp://hdl.handle.net/10754/608239en
dc.description.abstractWe investigate theoretically charge delocalization in radical-cations, i.e., positive polarons, formed on oligomer chains of poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene), PBTTT. We use non-empirically tuned range-separated density functionals (TRS-DFT), including LC-ωPBE, LC-BLYP, and ωB97XD. We consider the evolution with oligomer length of the molecular geometric and electronic structures, optical absorption features, and spin densities. The TRS-DFT results indicate that a positive polaron can delocalize ideally over some 10 thiophene rings when the backbone is non-planar and up to 14 rings for a backbone forced to be completely planar. Interestingly, up to six polarons can co-exist side-by-side in a hexamer (which contains 24 thiophene rings), which is consistent with the highest degrees of doping (oxidation) experimentally achievable in polythiophene derivatives.en
dc.description.sponsorshipThis work has been supported by King Abdullah University of Science and Technology (KAUST). We acknowledge the KAUST IT Research Computing Team for providing computational and storage resources and thank Dr. Cheng Zhong, Dr. Haitao Sun, and Dr. Bradley D. Rose for stimulating discussions.en
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.jpcc.6b02378en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.6b02378.en
dc.titleCharge Delocalization in Oligomers of Poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene), PBTTTen
dc.typeArticleen
dc.contributor.departmentSolar and Photovoltaic Engineering Research Center (SPERC)en
dc.identifier.journalThe Journal of Physical Chemistry Cen
dc.eprint.versionPost-printen
dc.contributor.institutionInstitut für Experimentalphysik Freie Universität Berlin D-14195 Berlin, Germanyen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorZhang, Yuexingen
kaust.authorBredas, Jean-Lucen
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