Impact of Charge-Resonance Excitations on CT-Mediated J-Type Aggregation in Singlet and Triplet Exciton States of Perylene Di-Imide Aggregates: A TDDFT Investigation

The modulation of intermolecular interactions upon aggregation induces changes in excited state properties of organic molecules that can be detrimental for some optoelectronic applications but can be exploited for others. The time-dependent density functional theory (TDDFT) is a cost-effective appro...

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Detalhes bibliográficos
Autores: Dai, Yasi, Zubiria Ulacia, María, Casanova Casas, David, Negri, Fabrizia
Formato: artículo
Fecha de publicación:2022
País:España
Recursos:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/55609
Acesso em linha:http://hdl.handle.net/10810/55609
Access Level:acceso abierto
Palavra-chave:molecular aggregates
singlet excitons
triplet excitons
TDDFT
charge-transfer states
charge-resonance states
Frenkel states
localized excitations
diabatic states
adiabatic states
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spelling Impact of Charge-Resonance Excitations on CT-Mediated J-Type Aggregation in Singlet and Triplet Exciton States of Perylene Di-Imide Aggregates: A TDDFT InvestigationDai, YasiZubiria Ulacia, MaríaCasanova Casas, DavidNegri, Fabriziamolecular aggregatessinglet excitonstriplet excitonsTDDFTcharge-transfer statescharge-resonance statesFrenkel stateslocalized excitationsdiabatic statesadiabatic statesThe modulation of intermolecular interactions upon aggregation induces changes in excited state properties of organic molecules that can be detrimental for some optoelectronic applications but can be exploited for others. The time-dependent density functional theory (TDDFT) is a cost-effective approach to determining the exciton states of molecular aggregates, and it has been shown to provide reliable results when coupled with the appropriate choice of the functional. Here we apply a general procedure to analyze the aggregates’ exciton states derived from TDDFT calculations in terms of diabatic states chosen to coincide with local (LE) and charge-transfer (CT) excitations within a restricted orbital space. We apply the approach to study energy profiles, interstate couplings, and the charge-transfer character of singlet and triplet exciton states of perylene di-imide aggregates (PDI). We focus on the intermolecular displacement along the longitudinal translation coordinate, which mimics different amounts of slip-stacking observed in PDI crystals. The analysis, in terms of symmetry-adapted Frenkel excitations (FE) and charge-resonance (CR) states and their interactions, discloses how the interchange of the H/J character for small longitudinal shifts, previously reported for singlet exciton states, also occurs for triplet excitons.This research was funded by Ministerio de Economía y Competitividad of Spain, grant number PID2019-109555GB-I00 and RED2018-102815-T and by Eusko Jaurlaritza, grant number PIBA19-0004.MDPI2022202220222022info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/55609reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoInglésinfo:eu-repo/grantAgreement/MINECO/PID2019-109555GB-I00/info:eu-repo/grantAgreement/MINECO/RED2018-102815-T/https://www.mdpi.com/2079-3197/10/2/18/htminfo:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by/3.0/es/2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).oai:addi.ehu.eus:10810/556092026-06-18T09:23:17Z
dc.title.none.fl_str_mv Impact of Charge-Resonance Excitations on CT-Mediated J-Type Aggregation in Singlet and Triplet Exciton States of Perylene Di-Imide Aggregates: A TDDFT Investigation
title Impact of Charge-Resonance Excitations on CT-Mediated J-Type Aggregation in Singlet and Triplet Exciton States of Perylene Di-Imide Aggregates: A TDDFT Investigation
spellingShingle Impact of Charge-Resonance Excitations on CT-Mediated J-Type Aggregation in Singlet and Triplet Exciton States of Perylene Di-Imide Aggregates: A TDDFT Investigation
Dai, Yasi
molecular aggregates
singlet excitons
triplet excitons
TDDFT
charge-transfer states
charge-resonance states
Frenkel states
localized excitations
diabatic states
adiabatic states
title_short Impact of Charge-Resonance Excitations on CT-Mediated J-Type Aggregation in Singlet and Triplet Exciton States of Perylene Di-Imide Aggregates: A TDDFT Investigation
title_full Impact of Charge-Resonance Excitations on CT-Mediated J-Type Aggregation in Singlet and Triplet Exciton States of Perylene Di-Imide Aggregates: A TDDFT Investigation
title_fullStr Impact of Charge-Resonance Excitations on CT-Mediated J-Type Aggregation in Singlet and Triplet Exciton States of Perylene Di-Imide Aggregates: A TDDFT Investigation
title_full_unstemmed Impact of Charge-Resonance Excitations on CT-Mediated J-Type Aggregation in Singlet and Triplet Exciton States of Perylene Di-Imide Aggregates: A TDDFT Investigation
title_sort Impact of Charge-Resonance Excitations on CT-Mediated J-Type Aggregation in Singlet and Triplet Exciton States of Perylene Di-Imide Aggregates: A TDDFT Investigation
dc.creator.none.fl_str_mv Dai, Yasi
Zubiria Ulacia, María
Casanova Casas, David
Negri, Fabrizia
author Dai, Yasi
author_facet Dai, Yasi
Zubiria Ulacia, María
Casanova Casas, David
Negri, Fabrizia
author_role author
author2 Zubiria Ulacia, María
Casanova Casas, David
Negri, Fabrizia
author2_role author
author
author
dc.subject.none.fl_str_mv molecular aggregates
singlet excitons
triplet excitons
TDDFT
charge-transfer states
charge-resonance states
Frenkel states
localized excitations
diabatic states
adiabatic states
topic molecular aggregates
singlet excitons
triplet excitons
TDDFT
charge-transfer states
charge-resonance states
Frenkel states
localized excitations
diabatic states
adiabatic states
description The modulation of intermolecular interactions upon aggregation induces changes in excited state properties of organic molecules that can be detrimental for some optoelectronic applications but can be exploited for others. The time-dependent density functional theory (TDDFT) is a cost-effective approach to determining the exciton states of molecular aggregates, and it has been shown to provide reliable results when coupled with the appropriate choice of the functional. Here we apply a general procedure to analyze the aggregates’ exciton states derived from TDDFT calculations in terms of diabatic states chosen to coincide with local (LE) and charge-transfer (CT) excitations within a restricted orbital space. We apply the approach to study energy profiles, interstate couplings, and the charge-transfer character of singlet and triplet exciton states of perylene di-imide aggregates (PDI). We focus on the intermolecular displacement along the longitudinal translation coordinate, which mimics different amounts of slip-stacking observed in PDI crystals. The analysis, in terms of symmetry-adapted Frenkel excitations (FE) and charge-resonance (CR) states and their interactions, discloses how the interchange of the H/J character for small longitudinal shifts, previously reported for singlet exciton states, also occurs for triplet excitons.
publishDate 2022
dc.date.none.fl_str_mv 2022
2022
2022
2022
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/55609
url http://hdl.handle.net/10810/55609
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/MINECO/PID2019-109555GB-I00/
info:eu-repo/grantAgreement/MINECO/RED2018-102815-T/
https://www.mdpi.com/2079-3197/10/2/18/htm
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by/3.0/es/
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by/3.0/es/
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv MDPI
publisher.none.fl_str_mv MDPI
dc.source.none.fl_str_mv reponame:Addi. Archivo Digital para la Docencia y la Investigación
instname:Universidad del País Vasco
instname_str Universidad del País Vasco
reponame_str Addi. Archivo Digital para la Docencia y la Investigación
collection Addi. Archivo Digital para la Docencia y la Investigación
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,301629

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