Ab-initio insight into the organic photochemical diversity: non-radiative decay in uracil and derivatives and intramolecular charge transfer mechanisms in the benzonitrile family

In this thesis, we studied two different types of photochemical reactions. On one hand, we determined non-radiative decay mechanisms for uracil molecule, which is part of the RNA. We then studied some derivatives of uracil (5-fluorouracil and 5- and 6-aminouracil) in order to explain their longer ex...

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Autor: Yannick, Mercier
Tipo de recurso: tesis doctoral
Estado:Versión publicada
Fecha de publicación:2011
País:España
Institución:Universitat Rovira i virgili (URV)
Repositorio:Repositori Institucional de la Universitat Rovira i Virgili
OAI Identifier:oai:urv.cat:TDX:947
Acceso en línea:https://hdl.handle.net/20.500.11797/TDX947
http://hdl.handle.net/10803/37341
Access Level:acceso abierto
Palabra clave:544 - Química física
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spelling Ab-initio insight into the organic photochemical diversity: non-radiative decay in uracil and derivatives and intramolecular charge transfer mechanisms in the benzonitrile familyYannick, Mercier544 - Química físicaIn this thesis, we studied two different types of photochemical reactions. On one hand, we determined non-radiative decay mechanisms for uracil molecule, which is part of the RNA. We then studied some derivatives of uracil (5-fluorouracil and 5- and 6-aminouracil) in order to explain their longer excited states lifetime relative to the parent system. It also allowed us to confirm our initial hypothesis. A second part of our work was about the Intramolecular Charge Transfer (ICT) in the benzonitrile family. Three derivatives of the DMABN have been studied: bicycle systems, 4F-DMABN and DTABN isomers. These systems allowed us to check both electronic and steric effects as well as to explain the mechanisms controlling the potential dual fluorescence and the emitting species. Our studies have been done using the CASSCF/CASPT2 method, with a good agreement with experimental results, which confirms the reliability of this method.En esta tesis, se ha estudiado dos tipos de reacciones fotoquímicas. Por una parte, se han determinado los mecanismos de reacciones de desactivación no radiativa en la molécula de Uracilo, que forma parte del ARN. Mediante el estudio de derivados del uracilo (5-fluorouracilo y 5- y 6-aminouracilo) se ha podido explicar por qué los derivados presentan estados excitados con tiempos de vida màs largos que el sistema original. También se ha estudiado la fotoquímica de la familia de los aminobenzonitrilos (biciclos, 4F-DMABN y los isomeros del DTABN). Se han determinado los mecanismos de la reacción de transferencia intramolecular de carga, con localización de las especies luminiscentes. Los diferentes derivados han permitido estudiar los efectos estericos y electrónicos y explicar los patrones de fluorescencia diferentes encontrados para los distintos derivados. Los estudios fueron realizados mediante el método CASSCF/CASPT2, con una buena adecuación a los resultados experimentales.Universitat Rovira i Virgili Departament de Química Física i InorgànicaUniversitat Rovira i Virgili.2011info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdf151 p.https://hdl.handle.net/20.500.11797/TDX947http://hdl.handle.net/10803/37341reponame:Repositori Institucional de la Universitat Rovira i Virgiliinstname:Universitat Rovira i virgili (URV)Inglésinfo:eu-repo/semantics/openAccessADVERTIMENT. L'accés als continguts d'aquesta tesi doctoral i la seva utilització ha de respectar els drets de la persona autora. Pot ser utilitzada per a consulta o estudi personal, així com en activitats o materials d'investigació i docència en els termes establerts a l'art. 32 del Text Refós de la Llei de Propietat Intel·lectual (RDL 1/1996). Per altres utilitzacions es requereix l'autorització prèvia i expressa de la persona autora. En qualsevol cas, en la utilització dels seus continguts caldrà  indicar de forma clara el nom i cognoms de la persona autora i el títol de la tesi doctoral. No s'autoritza la seva reproducció o altres formes d'explotació efectuades amb finalitats de lucre ni la seva comunicació pública des d'un lloc aliè al repositori institucional de la Universitat Rovira i Virgili. Tampoc s'autoritza la presentació del seu contingut en una finestra o marc aliè a aquest repositori (framing). Aquesta reserva de drets afecta tant als continguts de la tesi com als seus resums i índexs.oai:urv.cat:TDX:9472026-06-23T12:42:27Z
dc.title.none.fl_str_mv Ab-initio insight into the organic photochemical diversity: non-radiative decay in uracil and derivatives and intramolecular charge transfer mechanisms in the benzonitrile family
title Ab-initio insight into the organic photochemical diversity: non-radiative decay in uracil and derivatives and intramolecular charge transfer mechanisms in the benzonitrile family
spellingShingle Ab-initio insight into the organic photochemical diversity: non-radiative decay in uracil and derivatives and intramolecular charge transfer mechanisms in the benzonitrile family
Yannick, Mercier
544 - Química física
title_short Ab-initio insight into the organic photochemical diversity: non-radiative decay in uracil and derivatives and intramolecular charge transfer mechanisms in the benzonitrile family
title_full Ab-initio insight into the organic photochemical diversity: non-radiative decay in uracil and derivatives and intramolecular charge transfer mechanisms in the benzonitrile family
title_fullStr Ab-initio insight into the organic photochemical diversity: non-radiative decay in uracil and derivatives and intramolecular charge transfer mechanisms in the benzonitrile family
title_full_unstemmed Ab-initio insight into the organic photochemical diversity: non-radiative decay in uracil and derivatives and intramolecular charge transfer mechanisms in the benzonitrile family
title_sort Ab-initio insight into the organic photochemical diversity: non-radiative decay in uracil and derivatives and intramolecular charge transfer mechanisms in the benzonitrile family
dc.creator.none.fl_str_mv Yannick, Mercier
author Yannick, Mercier
author_facet Yannick, Mercier
author_role author
dc.contributor.none.fl_str_mv Departament de Química Física i Inorgànica
Universitat Rovira i Virgili.
dc.subject.none.fl_str_mv 544 - Química física
topic 544 - Química física
description In this thesis, we studied two different types of photochemical reactions. On one hand, we determined non-radiative decay mechanisms for uracil molecule, which is part of the RNA. We then studied some derivatives of uracil (5-fluorouracil and 5- and 6-aminouracil) in order to explain their longer excited states lifetime relative to the parent system. It also allowed us to confirm our initial hypothesis. A second part of our work was about the Intramolecular Charge Transfer (ICT) in the benzonitrile family. Three derivatives of the DMABN have been studied: bicycle systems, 4F-DMABN and DTABN isomers. These systems allowed us to check both electronic and steric effects as well as to explain the mechanisms controlling the potential dual fluorescence and the emitting species. Our studies have been done using the CASSCF/CASPT2 method, with a good agreement with experimental results, which confirms the reliability of this method.
publishDate 2011
dc.date.none.fl_str_mv 2011
dc.type.none.fl_str_mv info:eu-repo/semantics/publishedVersion
info:eu-repo/semantics/doctoralThesis
format doctoralThesis
status_str publishedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/20.500.11797/TDX947
http://hdl.handle.net/10803/37341
url https://hdl.handle.net/20.500.11797/TDX947
http://hdl.handle.net/10803/37341
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
151 p.
dc.publisher.none.fl_str_mv Universitat Rovira i Virgili
publisher.none.fl_str_mv Universitat Rovira i Virgili
dc.source.none.fl_str_mv reponame:Repositori Institucional de la Universitat Rovira i Virgili
instname:Universitat Rovira i virgili (URV)
instname_str Universitat Rovira i virgili (URV)
reponame_str Repositori Institucional de la Universitat Rovira i Virgili
collection Repositori Institucional de la Universitat Rovira i Virgili
repository.name.fl_str_mv
repository.mail.fl_str_mv
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