Explicit modelling of spectral bandshapes by a mixed quantum-classical approach: solvent order and temperature effects in the optical spectra of distryrylbenzene

The absorption and emission spectral shapes of a flexible organic probe, the distyrylbenzene (DSB) dye, are simulated accounting for the effect of different environments of increasing complexity, ranging from a homogeneous, low-molecular- weight solvent, to a long-chain alkane, and, eventually, a ch...

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Authors: Cerezo Bastida, Javier, Gierschner, Johannes, Santoro, Fabrizio, Prampolini, Giacomo
Format: article
Publication Date:2024
Country:España
Institution:Universidad Autónoma de Madrid
Repository:Biblos-e Archivo. Repositorio Institucional de la UAM
Language:English
OAI Identifier:oai:repositorio.uam.es:10486/714505
Online Access:http://hdl.handle.net/10486/714505
https://dx.doi.org/10.1002/cphc.202400307
Access Level:Open access
Keyword:computation of absorption and emission spectra
flexible dyes
mixed quantum classical approach
molecular dynamics and vibronic models
solvent and organic solid matrix
Química
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spelling Explicit modelling of spectral bandshapes by a mixed quantum-classical approach: solvent order and temperature effects in the optical spectra of distryrylbenzeneCerezo Bastida, JavierGierschner, JohannesSantoro, FabrizioPrampolini, Giacomocomputation of absorption and emission spectraflexible dyesmixed quantum classical approachmolecular dynamics and vibronic modelssolvent and organic solid matrixQuímicaThe absorption and emission spectral shapes of a flexible organic probe, the distyrylbenzene (DSB) dye, are simulated accounting for the effect of different environments of increasing complexity, ranging from a homogeneous, low-molecular- weight solvent, to a long-chain alkane, and, eventually, a channel-forming organic matrix. Each embedding is treated explicitly, adopting a mixed quantum-classical approach, the Adiabatic Molecular Dynamics – generalized vertical Hessian (Ad-MD|gVH) model, which allows a direct simulation of the environment-induced constraining effects on the vibronic spectral shapes. In such a theoretical framework, the stiff modes of the dye are described at a quantum level within the harmonic approximation, including Duschinsky mixing effects, while flexible degrees of freedom of the solute (e. g. torsions) and those of the solvent are treated classically by means of molecular dynamics sampling. Such a setup is shown to reproduce the distinct effects exerted by the different environments in varied thermodynamic conditions. Besides allowing for a first-principles rationale on the supramolecular mechanism leading to the experimental spectral features, this result represents the first successful application of the Ad-MD|gVH method to complex embeddings and supports its potential application to other heterogeneous environments, such as for instance, pigment-protein complexes or organic dyes adsorbed into metal-organic frameworks. F.\u2009S. and G.\u2009P. thank the support of ICSC \u2013 Centro Nazionale di Ricerca in High Performance Computing, Big Data and Quantum Computing, funded by European Union \u2013 NextGenerationEU \u2013 PNRR, Missione 4 Componente 2 Investimento 1.4. J.\u2009G. acknowledges funding by the Spanish Ministerio de Ciencia e Innovaci\u00F3n (MICIN\u2010FEDER project PID2022\u2010138222NB\u2010C21), by the Severo Ochoa program for Centers of Excellence in R&D of the MICIN (CEX2020\u2010001039\u2010S), and by the Campus of International Excellence (CEI) UAM+CSIC. J.\u2009C. thanks Ministerio de Universidades, Plan de Recuperaci\u00F3n, Transformaci\u00F3n y Resiliencia and UAM for funding the research stay in Pisa with a requalification program (CA2/RSUE/2021\u201000890) and the MICINN Project PID2019\u2010110091GB\u2010I00 for financial support. Computational resources provided by ICCOM and the Centro de C\u00E1lculo Cient\u00EDfico at Universidad Aut\u00F3noma de Madrid (CCC\u2010UAM) are also acknowledgedWileyDepartamento de QuímicaFacultad de Ciencias20242024-05-10research articlehttp://purl.org/coar/resource_type/c_2df8fbb1EVoRhttp://purl.org/coar/version/c_dc82b40f9837b551info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/714505https://dx.doi.org/10.1002/cphc.202400307reponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/7145052026-06-23T12:46:27Z
dc.title.none.fl_str_mv Explicit modelling of spectral bandshapes by a mixed quantum-classical approach: solvent order and temperature effects in the optical spectra of distryrylbenzene
title Explicit modelling of spectral bandshapes by a mixed quantum-classical approach: solvent order and temperature effects in the optical spectra of distryrylbenzene
spellingShingle Explicit modelling of spectral bandshapes by a mixed quantum-classical approach: solvent order and temperature effects in the optical spectra of distryrylbenzene
Cerezo Bastida, Javier
computation of absorption and emission spectra
flexible dyes
mixed quantum classical approach
molecular dynamics and vibronic models
solvent and organic solid matrix
Química
title_short Explicit modelling of spectral bandshapes by a mixed quantum-classical approach: solvent order and temperature effects in the optical spectra of distryrylbenzene
title_full Explicit modelling of spectral bandshapes by a mixed quantum-classical approach: solvent order and temperature effects in the optical spectra of distryrylbenzene
title_fullStr Explicit modelling of spectral bandshapes by a mixed quantum-classical approach: solvent order and temperature effects in the optical spectra of distryrylbenzene
title_full_unstemmed Explicit modelling of spectral bandshapes by a mixed quantum-classical approach: solvent order and temperature effects in the optical spectra of distryrylbenzene
title_sort Explicit modelling of spectral bandshapes by a mixed quantum-classical approach: solvent order and temperature effects in the optical spectra of distryrylbenzene
dc.creator.none.fl_str_mv Cerezo Bastida, Javier
Gierschner, Johannes
Santoro, Fabrizio
Prampolini, Giacomo
author Cerezo Bastida, Javier
author_facet Cerezo Bastida, Javier
Gierschner, Johannes
Santoro, Fabrizio
Prampolini, Giacomo
author_role author
author2 Gierschner, Johannes
Santoro, Fabrizio
Prampolini, Giacomo
author2_role author
author
author
dc.contributor.none.fl_str_mv Departamento de Química
Facultad de Ciencias
dc.subject.none.fl_str_mv computation of absorption and emission spectra
flexible dyes
mixed quantum classical approach
molecular dynamics and vibronic models
solvent and organic solid matrix
Química
topic computation of absorption and emission spectra
flexible dyes
mixed quantum classical approach
molecular dynamics and vibronic models
solvent and organic solid matrix
Química
description The absorption and emission spectral shapes of a flexible organic probe, the distyrylbenzene (DSB) dye, are simulated accounting for the effect of different environments of increasing complexity, ranging from a homogeneous, low-molecular- weight solvent, to a long-chain alkane, and, eventually, a channel-forming organic matrix. Each embedding is treated explicitly, adopting a mixed quantum-classical approach, the Adiabatic Molecular Dynamics – generalized vertical Hessian (Ad-MD|gVH) model, which allows a direct simulation of the environment-induced constraining effects on the vibronic spectral shapes. In such a theoretical framework, the stiff modes of the dye are described at a quantum level within the harmonic approximation, including Duschinsky mixing effects, while flexible degrees of freedom of the solute (e. g. torsions) and those of the solvent are treated classically by means of molecular dynamics sampling. Such a setup is shown to reproduce the distinct effects exerted by the different environments in varied thermodynamic conditions. Besides allowing for a first-principles rationale on the supramolecular mechanism leading to the experimental spectral features, this result represents the first successful application of the Ad-MD|gVH method to complex embeddings and supports its potential application to other heterogeneous environments, such as for instance, pigment-protein complexes or organic dyes adsorbed into metal-organic frameworks
publishDate 2024
dc.date.none.fl_str_mv 2024
2024-05-10
dc.type.none.fl_str_mv research article
http://purl.org/coar/resource_type/c_2df8fbb1
EVoR
http://purl.org/coar/version/c_dc82b40f9837b551
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10486/714505
https://dx.doi.org/10.1002/cphc.202400307
url http://hdl.handle.net/10486/714505
https://dx.doi.org/10.1002/cphc.202400307
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv reponame:Biblos-e Archivo. Repositorio Institucional de la UAM
instname:Universidad Autónoma de Madrid
instname_str Universidad Autónoma de Madrid
reponame_str Biblos-e Archivo. Repositorio Institucional de la UAM
collection Biblos-e Archivo. Repositorio Institucional de la UAM
repository.name.fl_str_mv
repository.mail.fl_str_mv
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