From wavelike to sub-diffusive motion: exciton dynamics and interaction in squaraine copolymers of varying length.
Journal
Chemical science
ISSN: 2041-6520
Titre abrégé: Chem Sci
Pays: England
ID NLM: 101545951
Informations de publication
Date de publication:
18 Nov 2019
18 Nov 2019
Historique:
entrez:
4
6
2021
pubmed:
18
11
2019
medline:
18
11
2019
Statut:
epublish
Résumé
Exciton transport and exciton-exciton interactions in molecular aggregates and polymers are of great importance in natural photosynthesis, organic electronics, and related areas of research. Both the experimental observation and theoretical description of these processes across time and length scales, including the transition from the initial wavelike motion to the following long-range exciton transport, are highly challenging. Therefore, while exciton dynamics at small scales are often treated explicitly, long-range exciton transport is typically described phenomenologically by normal diffusion. In this work, we study the transition from wavelike to diffusive motion of interacting exciton pairs in squaraine copolymers of varying length. To this end we use a combination of the recently introduced exciton-exciton-interaction two-dimensional (EEI2D) electronic spectroscopy and microscopic theoretical modelling. As we show by comparison with the model, the experimentally observed kinetics include three phases, wavelike motion dominated by immediate exciton-exciton annihilation (10-100 fs), sub-diffusive behavior (0.1-10 ps), and excitation relaxation (0.01-1 ns). We demonstrate that the key quantity for the transition from wavelike to diffusive dynamics is the exciton delocalization length relative to the length of the polymer: while in short polymers wavelike motion of rapidly annihilating excitons dominates, in long polymers the excitons become locally trapped and exhibit sub-diffusive behavior. Our findings indicate that exciton transport through conjugated systems emerging from the excitonic structure is generally not governed by normal diffusion. Instead, to characterize the material transport properties, the diffusion presence and character should be determined.
Identifiants
pubmed: 34084345
doi: 10.1039/c9sc04367e
pii: c9sc04367e
pmc: PMC8146531
doi:
Types de publication
Journal Article
Langues
eng
Pagination
456-466Commentaires et corrections
Type : ErratumIn
Informations de copyright
This journal is © The Royal Society of Chemistry.
Déclaration de conflit d'intérêts
There are no conflicts to declare.
Références
J Am Chem Soc. 2014 Feb 12;136(6):2351-62
pubmed: 24432873
J Chem Phys. 2016 Oct 28;145(16):164907
pubmed: 27802628
Philos Trans A Math Phys Eng Sci. 2012 Aug 13;370(1972):3750-70
pubmed: 22753824
J Phys Chem A. 2015 Nov 5;119(44):10893-909
pubmed: 26463085
Faraday Discuss. 2019 Dec 16;221(0):265-280
pubmed: 31538634
J Phys Chem B. 2013 Dec 12;117(49):15257-71
pubmed: 23895366
J Chem Phys. 2012 May 28;136(20):204503
pubmed: 22667567
Nat Commun. 2014 Apr 16;5:3646
pubmed: 24736470
Acc Chem Res. 2009 Nov 17;42(11):1691-9
pubmed: 19653630
J Phys Chem Lett. 2014 Feb 6;5(3):622-32
pubmed: 26276619
Annu Rev Phys Chem. 2015 Apr;66:667-90
pubmed: 25664841
Nature. 2005 Mar 31;434(7033):625-8
pubmed: 15800619
Nat Chem. 2011 Sep 23;3(10):763-74
pubmed: 21941248
Nat Chem. 2016 Jan;8(1):16-23
pubmed: 26673260
J Chem Phys. 2016 Sep 28;145(12):124312
pubmed: 27782618
J Chem Phys. 2014 Jun 28;140(24):244108
pubmed: 24985619
Photosynth Res. 2009 Aug-Sep;101(2-3):105-18
pubmed: 19578970
Nat Commun. 2018 Jun 25;9(1):2466
pubmed: 29941915
Phys Chem Chem Phys. 2014 May 14;16(18):8193-200
pubmed: 24676396
J Phys Chem Lett. 2015 Sep 3;6(17):3417-28
pubmed: 26269208
J Chem Phys. 2004 Feb 1;120(5):2325-36
pubmed: 15268371
J Phys Chem A. 2011 Feb 10;115(5):648-54
pubmed: 21192672
J Phys Chem B. 2013 Dec 12;117(49):15369-85
pubmed: 23808641
Nat Chem. 2016 Jul;8(7):705-10
pubmed: 27325098
Annu Rev Phys Chem. 2014;65:127-48
pubmed: 24313684
J Am Chem Soc. 2015 Jun 24;137(24):7851-61
pubmed: 26016517
Phys Chem Chem Phys. 2016 May 11;18(19):13368-74
pubmed: 27120976
Nat Commun. 2019 Oct 10;10(1):4615
pubmed: 31601795
J Chem Phys. 2019 Mar 14;150(10):104304
pubmed: 30876358
Acc Chem Res. 2009 Sep 15;42(9):1352-63
pubmed: 19691358
Chem Rev. 2018 Aug 8;118(15):7069-7163
pubmed: 29664617
Science. 2009 May 29;324(5931):1169-73
pubmed: 19478176
Annu Rev Phys Chem. 2019 Jun 14;70:219-244
pubmed: 30883273
Proc Natl Acad Sci U S A. 2007 Sep 4;104(36):14190-6
pubmed: 17664429
Annu Rev Phys Chem. 2003;54:425-63
pubmed: 12626736
Adv Mater. 2013 Jun 4;25(21):2943-7
pubmed: 23580394
J Phys Chem B. 2009 Dec 24;113(51):16409-19
pubmed: 19954155
Science. 2018 May 25;360(6391):897-900
pubmed: 29798881