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AbstractAbstract
[en] This research thesis reports the study of a styrenic laser dye, the 4-(dicyanomethylene)-2-methyl-6-[p-(dimethylamino) styryl]-4H-pyrane or DCM for the characterization of the first electronic states and of the influence of the solvent on efficiencies of different relaxation processes of the first excited state S1 of the DCM. Due to the presence of a combination of a donor group and acceptor group, this compound has interesting properties of intra-molecular charge transfer and of photo-isomerization which highly depend on solvent polarity. Two approaches have been adopted to study these complementary processes: an experimental approach (determination of rate constants of the different deactivation ways of the S1 state by measuring fluorescence quantum efficiencies, photo-isomerization quantum efficiencies, and fluorescence lifetimes of DCM in about twenty solvent of increasing polarity), and a computational approach (a CS-INDO-MRI type quantum chemistry calculation to obtain potential energy curves, charge distributions, and dipolar moments of DCM first electronic states)
[fr]
Cette etude du colorant laser styrenique 4-(dicyanomethylene)-2-methyl-6-[p- (dimethylamino) styryl]-4H-pyrane ou DCM nous a permis de caracteriser la nature des premiers etats electroniques et l'influence du solvant sur les efficacites des differents processus de relaxation du premier etat excite S1 du DCM. Le DCM qui possede un groupe donneur d'electron conjugue par une serie de doubles liaisons avec un groupe accepteur d'electron presente d'interessantes proprietes de transfert de charge intramoleculaire et de photoisomerisation qui dependent grandement de la polarite du solvant. Afin de caracteriser ces deux processus elementaires, nous avons utilise deux approches complementaires. 1) Experimentalement, les constantes de vitesse des differentes voies de desactivation de l'etat S1 ont ete determinees en mesurant les rendements quantiques de fluorescence, les rendements quantiques de photoisomerisation et les durees de vie de fluorescence du DCM dans une vingtaine de solvants de polarite croissante. 2) Des calculs de chimie quantique du type CS/INDO/MRCI nous ont permis d'obtenir les courbes d'energie potentielle, les repartitions de charge et les moments dipolaires des premiers etats electroniques du DCM en considerant tous les changements de conformation pouvant eventuellement etre impliques dans les differents processus de relaxation de l'etat excite S1. (auteur)Original Title
Etude theorique et experimentale de la relaxation des etats excites du colorant laser DCM. Transfert d'electron intramoleculaire et photoisomerisation. Effets de solvant
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Source
23 Jan 1992; 216 p; 41 refs.; Available from the INIS Liaison Officer for France, see the 'INIS contacts' section of the INIS web site for current contact and E-mail addresses: http://www.iaea.org/inis/Contacts/; These Docteur en Science
Record Type
Miscellaneous
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Thesis/Dissertation
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Country of publication
CALCULATION METHODS, CHARGE TRANSPORT, DE-EXCITATION, DIPOLE MOMENTS, DYES, ELECTRON TRANSFER, ELECTRONIC STRUCTURE, EXCITED STATES, FLUORESCENCE, ISOMERIZATION, LIQUID LASERS, MOLECULAR STRUCTURE, PHOTOCHEMICAL REACTIONS, PHOTOCHEMISTRY, POTENTIAL ENERGY, RELAXATION, SOLUBILITY, SOLUTES, SOLVENTS, STYRENE
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