Cost-Effective Simulations of Vibrationally-Resolved Absorption Spectra of Fluorophores with Machine-Learning-Based Inhomogeneous Broadening

The results of electronic and vibrational structure simulations are an invaluable support for interpreting experimental absorption/emission spectra, which stimulates the development of reliable and cost-effective computational protocols. In this work, we contribute to these efforts and propose an ef...

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Autores: Petrusevich, Elizaveta F., Bousquet, Manon H. E., Ośmiałowski, Borys, Jacquemin, Denis, Luis Luis, Josep Maria, Zaleśny, Robert
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/23282
Acceso en línea:http://hdl.handle.net/10256/23282
Access Level:acceso abierto
Palabra clave:Espectres d'absorció
Espectres vibracionals
Absorption spectra
Vibrational spectra
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spelling Cost-Effective Simulations of Vibrationally-Resolved Absorption Spectra of Fluorophores with Machine-Learning-Based Inhomogeneous BroadeningPetrusevich, Elizaveta F.Bousquet, Manon H. E.Ośmiałowski, BorysJacquemin, DenisLuis Luis, Josep MariaZaleśny, RobertEspectres d'absorcióEspectres vibracionalsAbsorption spectraVibrational spectraThe results of electronic and vibrational structure simulations are an invaluable support for interpreting experimental absorption/emission spectra, which stimulates the development of reliable and cost-effective computational protocols. In this work, we contribute to these efforts and propose an efficient first-principle protocol for simulating vibrationally-resolved absorption spectra, including nonempirical estimations of the inhomogeneous broadening. To this end, we analyze three key aspects: (i) a metric-based selection of density functional approximation (DFA) so to benefit from the computational efficiency of time-dependent density function theory (TD-DFT) while safeguarding the accuracy of the vibrationally-resolved spectra, (ii) an assessment of two vibrational structure schemes (vertical gradient and adiabatic Hessian) to compute the Franck-Condon factors, and (iii) the use of machine learning to speed up nonempirical estimations of the inhomogeneous broadening. In more detail, we predict the absorption band shapes for a set of 20 medium-sized fluorescent dyes, focusing on the bright ππ★ S0 → S1 transition and using experimental results as references. We demonstrate that, for the studied 20-dye set which includes structures with large structural variability, the preselection of DFAs based on an easily accessible metric ensures accurate band shapes with respect to the reference approach and that range-separated functionals show the best performance when combined with the vertical gradient model. As far as band widths are concerned, we propose a new machine-learning-based approach for determining the inhomogeneous broadening induced by the solvent microenvironment. This approach is shown to be very robust offering inhomogeneous broadenings with errors as small as 2 cm-1 with respect to genuine electronic-structure calculations, with a total CPU time reduced by 98%E.F.P. and R.Z. gratefully acknowledge the support from the National Science Centre, Poland (Grant No. 2018/30/E/ST4/00457). J.-M.L. thanks the Spanish Ministry of Science (PGC2018-098212-B-C22) and Generalitat de Catalunya (2021SGR00623) for financial supportAmerican Chemical Society (ACS)Agencia Estatal de Investigación2023info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionpeer-reviewed12 p.application/pdfhttp://hdl.handle.net/10256/23282http://hdl.handle.net/10256/23282Journal of Chemical Theory and Computation, 2023, vol. 19, núm. 8, p. 2304-2315Articles publicats (D-Q)Petrusevich, Elizaveta F. Bousquet, Manon H. E. O&#347mia&#322owski, Borys Jacquemin, Denis Luis Luis, Josep Maria Zale&#347ny, Robert 2023 Cost-Effective Simulations of Vibrationally-Resolved Absorption Spectra of Fluorophores with Machine-Learning-Based Inhomogeneous Broadening Journal of Chemical Theory and Computation 19 8 2304 2315reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jctc.2c01285info:eu-repo/semantics/altIdentifier/issn/1549-9618info:eu-repo/semantics/altIdentifier/eissn/1549-9626info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-098212-B-C22Reconeixement 4.0 Internacionalhttp://creativecommons.org/licenses/by/4.0info:eu-repo/semantics/openAccessoai:recercat.cat:10256/232822026-05-29T05:05:01Z
dc.title.none.fl_str_mv Cost-Effective Simulations of Vibrationally-Resolved Absorption Spectra of Fluorophores with Machine-Learning-Based Inhomogeneous Broadening
title Cost-Effective Simulations of Vibrationally-Resolved Absorption Spectra of Fluorophores with Machine-Learning-Based Inhomogeneous Broadening
spellingShingle Cost-Effective Simulations of Vibrationally-Resolved Absorption Spectra of Fluorophores with Machine-Learning-Based Inhomogeneous Broadening
Petrusevich, Elizaveta F.
Espectres d'absorció
Espectres vibracionals
Absorption spectra
Vibrational spectra
title_short Cost-Effective Simulations of Vibrationally-Resolved Absorption Spectra of Fluorophores with Machine-Learning-Based Inhomogeneous Broadening
title_full Cost-Effective Simulations of Vibrationally-Resolved Absorption Spectra of Fluorophores with Machine-Learning-Based Inhomogeneous Broadening
title_fullStr Cost-Effective Simulations of Vibrationally-Resolved Absorption Spectra of Fluorophores with Machine-Learning-Based Inhomogeneous Broadening
title_full_unstemmed Cost-Effective Simulations of Vibrationally-Resolved Absorption Spectra of Fluorophores with Machine-Learning-Based Inhomogeneous Broadening
title_sort Cost-Effective Simulations of Vibrationally-Resolved Absorption Spectra of Fluorophores with Machine-Learning-Based Inhomogeneous Broadening
dc.creator.none.fl_str_mv Petrusevich, Elizaveta F.
Bousquet, Manon H. E.
Ośmiałowski, Borys
Jacquemin, Denis
Luis Luis, Josep Maria
Zaleśny, Robert
author Petrusevich, Elizaveta F.
author_facet Petrusevich, Elizaveta F.
Bousquet, Manon H. E.
Ośmiałowski, Borys
Jacquemin, Denis
Luis Luis, Josep Maria
Zaleśny, Robert
author_role author
author2 Bousquet, Manon H. E.
Ośmiałowski, Borys
Jacquemin, Denis
Luis Luis, Josep Maria
Zaleśny, Robert
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Agencia Estatal de Investigación
dc.subject.none.fl_str_mv Espectres d'absorció
Espectres vibracionals
Absorption spectra
Vibrational spectra
topic Espectres d'absorció
Espectres vibracionals
Absorption spectra
Vibrational spectra
description The results of electronic and vibrational structure simulations are an invaluable support for interpreting experimental absorption/emission spectra, which stimulates the development of reliable and cost-effective computational protocols. In this work, we contribute to these efforts and propose an efficient first-principle protocol for simulating vibrationally-resolved absorption spectra, including nonempirical estimations of the inhomogeneous broadening. To this end, we analyze three key aspects: (i) a metric-based selection of density functional approximation (DFA) so to benefit from the computational efficiency of time-dependent density function theory (TD-DFT) while safeguarding the accuracy of the vibrationally-resolved spectra, (ii) an assessment of two vibrational structure schemes (vertical gradient and adiabatic Hessian) to compute the Franck-Condon factors, and (iii) the use of machine learning to speed up nonempirical estimations of the inhomogeneous broadening. In more detail, we predict the absorption band shapes for a set of 20 medium-sized fluorescent dyes, focusing on the bright ππ★ S0 → S1 transition and using experimental results as references. We demonstrate that, for the studied 20-dye set which includes structures with large structural variability, the preselection of DFAs based on an easily accessible metric ensures accurate band shapes with respect to the reference approach and that range-separated functionals show the best performance when combined with the vertical gradient model. As far as band widths are concerned, we propose a new machine-learning-based approach for determining the inhomogeneous broadening induced by the solvent microenvironment. This approach is shown to be very robust offering inhomogeneous broadenings with errors as small as 2 cm-1 with respect to genuine electronic-structure calculations, with a total CPU time reduced by 98%
publishDate 2023
dc.date.none.fl_str_mv 2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
peer-reviewed
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/23282
http://hdl.handle.net/10256/23282
url http://hdl.handle.net/10256/23282
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jctc.2c01285
info:eu-repo/semantics/altIdentifier/issn/1549-9618
info:eu-repo/semantics/altIdentifier/eissn/1549-9626
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-098212-B-C22
dc.rights.none.fl_str_mv Reconeixement 4.0 Internacional
http://creativecommons.org/licenses/by/4.0
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Reconeixement 4.0 Internacional
http://creativecommons.org/licenses/by/4.0
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 12 p.
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society (ACS)
publisher.none.fl_str_mv American Chemical Society (ACS)
dc.source.none.fl_str_mv Journal of Chemical Theory and Computation, 2023, vol. 19, núm. 8, p. 2304-2315
Articles publicats (D-Q)
Petrusevich, Elizaveta F. Bousquet, Manon H. E. O&#347mia&#322owski, Borys Jacquemin, Denis Luis Luis, Josep Maria Zale&#347ny, Robert 2023 Cost-Effective Simulations of Vibrationally-Resolved Absorption Spectra of Fluorophores with Machine-Learning-Based Inhomogeneous Broadening Journal of Chemical Theory and Computation 19 8 2304 2315
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,812429

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