Excited states of bromopyrimidines probed by vuv photoabsorption spectroscopy and theoretical calculations

Bibliographic Details
Main Author: Mendes, Mónica
Publication Date: 2021
Other Authors: Kossoski, Fábris, Lozano, Ana I., Pereira‐da‐silva, João, Rodrigues, Rodrigo, Ameixa, João, Jones, Nykola C., Hoffmann, Søren V., da Silva, Filipe Ferreira
Format: Article
Language: eng
Source: Repositórios Científicos de Acesso Aberto de Portugal (RCAAP)
Download full: http://hdl.handle.net/10362/125427
Summary: PTDC/FIS‐ AQM/31281/2017 PD/00193/2012
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spelling Excited states of bromopyrimidines probed by vuv photoabsorption spectroscopy and theoretical calculationsHalopyrimidinesRadiosensitizersTime‐dependent density functional theoryValence and Rydberg statesVUV photoabsorptionCatalysisMolecular BiologySpectroscopyComputer Science ApplicationsPhysical and Theoretical ChemistryOrganic ChemistryInorganic ChemistryPTDC/FIS‐ AQM/31281/2017 PD/00193/2012We report absolute photoabsorption cross sections for gas‐phase 2‐ and 5‐ bromopyrimidine in the 3.7–10.8 eV energy range, in a joint theoretical and experimental study. The measurements were carried out using high‐resolution vacuum ultraviolet synchrotron radiation, with quantum chemical calculations performed through the nuclear ensemble approach in combination with time‐dependent density functional theory, along with additional Franck–Condon Herzberg–Teller calculations for the first absorption band (3.7–4.6 eV). The cross sections of both bromopyrimidines are very similar below 7.3 eV, deviating more substantially from each other at higher energies. In the 7.3–9.0 eV range where the maximum cross‐section is found, a single and broad band is observed for 5‐bromopyrimidine, while more discernible features appear in the case of 2‐bromopyrimidine. Several π* ← π transitions account for the most intense bands, while weaker ones are assigned to transitions involving the nitrogen and bromine lone pairs, the antibonding σ*Br orbital, and the lower‐lying Rydberg states. A detailed comparison with the available photo‐absorption data of bromobenzene is also reported. We have found significant differences regarding the main absorption band, which is more peaked in bromobenzene, becoming broader and shifting to higher energies in both bromopyrimidines. In addition, there is a significant suppression of vibrational structures and of Rydberg states in the pair of isomers, most noticeably for 2‐bromopyrimidine.CeFITec – Centro de Física e Investigação TecnológicaDF – Departamento de FísicaRUNMendes, MónicaKossoski, FábrisLozano, Ana I.Pereira‐da‐silva, JoãoRodrigues, RodrigoAmeixa, JoãoJones, Nykola C.Hoffmann, Søren V.da Silva, Filipe Ferreira2021-10-01T02:38:42Z2021-06-162021-06-16T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10362/125427eng1661-6596PURE: 34020120https://doi.org/10.3390/ijms22126460info:eu-repo/semantics/openAccessreponame:Repositórios Científicos de Acesso Aberto de Portugal (RCAAP)instname:FCCN, serviços digitais da FCT – Fundação para a Ciência e a Tecnologiainstacron:RCAAP2024-05-22T17:56:28Zoai:run.unl.pt:10362/125427Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireinfo@rcaap.ptopendoar:https://opendoar.ac.uk/repository/71602025-05-28T17:27:37.108719Repositórios Científicos de Acesso Aberto de Portugal (RCAAP) - FCCN, serviços digitais da FCT – Fundação para a Ciência e a Tecnologiafalse
dc.title.none.fl_str_mv Excited states of bromopyrimidines probed by vuv photoabsorption spectroscopy and theoretical calculations
title Excited states of bromopyrimidines probed by vuv photoabsorption spectroscopy and theoretical calculations
spellingShingle Excited states of bromopyrimidines probed by vuv photoabsorption spectroscopy and theoretical calculations
Mendes, Mónica
Halopyrimidines
Radiosensitizers
Time‐dependent density functional theory
Valence and Rydberg states
VUV photoabsorption
Catalysis
Molecular Biology
Spectroscopy
Computer Science Applications
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
title_short Excited states of bromopyrimidines probed by vuv photoabsorption spectroscopy and theoretical calculations
title_full Excited states of bromopyrimidines probed by vuv photoabsorption spectroscopy and theoretical calculations
title_fullStr Excited states of bromopyrimidines probed by vuv photoabsorption spectroscopy and theoretical calculations
title_full_unstemmed Excited states of bromopyrimidines probed by vuv photoabsorption spectroscopy and theoretical calculations
title_sort Excited states of bromopyrimidines probed by vuv photoabsorption spectroscopy and theoretical calculations
author Mendes, Mónica
author_facet Mendes, Mónica
Kossoski, Fábris
Lozano, Ana I.
Pereira‐da‐silva, João
Rodrigues, Rodrigo
Ameixa, João
Jones, Nykola C.
Hoffmann, Søren V.
da Silva, Filipe Ferreira
author_role author
author2 Kossoski, Fábris
Lozano, Ana I.
Pereira‐da‐silva, João
Rodrigues, Rodrigo
Ameixa, João
Jones, Nykola C.
Hoffmann, Søren V.
da Silva, Filipe Ferreira
author2_role author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv CeFITec – Centro de Física e Investigação Tecnológica
DF – Departamento de Física
RUN
dc.contributor.author.fl_str_mv Mendes, Mónica
Kossoski, Fábris
Lozano, Ana I.
Pereira‐da‐silva, João
Rodrigues, Rodrigo
Ameixa, João
Jones, Nykola C.
Hoffmann, Søren V.
da Silva, Filipe Ferreira
dc.subject.por.fl_str_mv Halopyrimidines
Radiosensitizers
Time‐dependent density functional theory
Valence and Rydberg states
VUV photoabsorption
Catalysis
Molecular Biology
Spectroscopy
Computer Science Applications
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
topic Halopyrimidines
Radiosensitizers
Time‐dependent density functional theory
Valence and Rydberg states
VUV photoabsorption
Catalysis
Molecular Biology
Spectroscopy
Computer Science Applications
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
description PTDC/FIS‐ AQM/31281/2017 PD/00193/2012
publishDate 2021
dc.date.none.fl_str_mv 2021-10-01T02:38:42Z
2021-06-16
2021-06-16T00:00:00Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
format article
status_str publishedVersion
dc.identifier.uri.fl_str_mv http://hdl.handle.net/10362/125427
url http://hdl.handle.net/10362/125427
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv 1661-6596
PURE: 34020120
https://doi.org/10.3390/ijms22126460
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:Repositórios Científicos de Acesso Aberto de Portugal (RCAAP)
instname:FCCN, serviços digitais da FCT – Fundação para a Ciência e a Tecnologia
instacron:RCAAP
instname_str FCCN, serviços digitais da FCT – Fundação para a Ciência e a Tecnologia
instacron_str RCAAP
institution RCAAP
reponame_str Repositórios Científicos de Acesso Aberto de Portugal (RCAAP)
collection Repositórios Científicos de Acesso Aberto de Portugal (RCAAP)
repository.name.fl_str_mv Repositórios Científicos de Acesso Aberto de Portugal (RCAAP) - FCCN, serviços digitais da FCT – Fundação para a Ciência e a Tecnologia
repository.mail.fl_str_mv info@rcaap.pt
_version_ 1833596708847616000

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