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dc.contributor.author
Freixas Lemus, Victor Manuel  
dc.contributor.author
Wilhelm, Philipp  
dc.contributor.author
Nelson, Tammie  
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Hinderer, Florian  
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Höger, Sigurd  
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Tretiak, Sergei  
dc.contributor.author
Lupton, John M.  
dc.contributor.author
Fernández Alberti, Sebastián  
dc.date.available
2022-08-23T18:20:42Z  
dc.date.issued
2021-09  
dc.identifier.citation
Freixas Lemus, Victor Manuel; Wilhelm, Philipp; Nelson, Tammie; Hinderer, Florian; Höger, Sigurd; et al.; Excitation Energy Transfer between bodipy Dyes in a Symmetric Molecular Excitonic Seesaw; American Chemical Society; Journal of Physical Chemistry A; 125; 38; 9-2021; 8404-8416  
dc.identifier.issn
1089-5639  
dc.identifier.uri
http://hdl.handle.net/11336/166383  
dc.description.abstract
We examine the redistribution of energy between electronic and vibrational degrees of freedom that takes place between a π-conjugated oligomer, a phenylene-butadiynylene, and two identical boron-dipyrromethene (bodipy) end-caps using femtosecond transient absorption spectroscopy, single-molecule spectroscopy, and nonadiabatic excited-state molecular dynamics (NEXMD) modeling techniques. The molecular structure represents an excitonic seesaw in that the excitation energy on the oligomer backbone can migrate to either one end-cap or the other, but not to both. The NEXMD simulations closely reproduce the characteristic time scale for redistribution of electronic and vibrational energy of 2.2 ps and uncover the vibrational modes contributing to the intramolecular relaxation. The calculations indicate that the dihedral angle between the bodipy dye and the oligomer change upon excitation of the oligomer. Single-molecule experiments reveal a difference in photoluminescence lifetime of the bodipy dyes depending on whether they are excited by direct absorption or by redistribution of energy from the backbone. This difference in lifetime may be attributed to the difference in dihedral angle. The simulations also suggest that a strong coupling can occur between the two end-caps, giving rise to a reversible shuttling of excitation energy between them. Strong coupling should lead to a pronounced loss in polarization memory of the fluorescence since the oligomer backbone tends to be slightly distorted and the two bodipy transition dipoles have different orientations. A sensitive single-molecule technique is presented to test for such coupling. However, although redistribution of electronic and vibrational energy between the end-caps can occur, it appears to be unidirectional and irreversible, suggesting that an additional localization mechanism is at play which is, as yet, not fully accounted for in the simulations.  
dc.format
application/pdf  
dc.language.iso
eng  
dc.publisher
American Chemical Society  
dc.rights
info:eu-repo/semantics/restrictedAccess  
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/  
dc.subject
Dinamica molecular no adiabática  
dc.subject
Transferencia de energía  
dc.subject.classification
Física Atómica, Molecular y Química  
dc.subject.classification
Ciencias Físicas  
dc.subject.classification
CIENCIAS NATURALES Y EXACTAS  
dc.title
Excitation Energy Transfer between bodipy Dyes in a Symmetric Molecular Excitonic Seesaw  
dc.type
info:eu-repo/semantics/article  
dc.type
info:ar-repo/semantics/artículo  
dc.type
info:eu-repo/semantics/publishedVersion  
dc.date.updated
2022-08-19T14:44:15Z  
dc.journal.volume
125  
dc.journal.number
38  
dc.journal.pagination
8404-8416  
dc.journal.pais
Estados Unidos  
dc.journal.ciudad
Washington  
dc.description.fil
Fil: Freixas Lemus, Victor Manuel. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina  
dc.description.fil
Fil: Wilhelm, Philipp. Universitat Regensburg; Alemania  
dc.description.fil
Fil: Nelson, Tammie. Los Alamos National Laboratory; Estados Unidos  
dc.description.fil
Fil: Hinderer, Florian. Universitat Regensburg; Alemania  
dc.description.fil
Fil: Höger, Sigurd. Universitat Regensburg; Alemania  
dc.description.fil
Fil: Tretiak, Sergei. Los Alamos National Laboratory; Estados Unidos  
dc.description.fil
Fil: Lupton, John M.. Universitat Regensburg; Alemania  
dc.description.fil
Fil: Fernández Alberti, Sebastián. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina  
dc.journal.title
Journal of Physical Chemistry A  
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpca.1c06332  
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/acs.jpca.1c06332