Orientador: Claudio Francisco Tormena / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T02:29:08Z (GMT). No. of bitstreams: 1 Favaro_DenizeCristina_D.pdf: 6372818 bytes, checksum: c89cc5eb491bd0129e563fc2dd200aac (MD5) Previous issue date: 2014 / Resumo: A tese "Estudo dos mecanismos de transmissão dos acoplamentos escalares via ligações e/ou via nuvem eletrônica próxima no espaço e estudos de difusão (DOSY) de 19F" é composta de 5 capítulos. O primeiro capítulo é uma visão geral sobre Ressonância Magnética Nuclear (RMN), sequências de pulso para determinação experimental das constantes de acoplamento, mecanismos envolvidos na transmissão desse importante parâmetro de RMN e Teoria dos Orbitais Naturais de Ligação (NBO). No segundo capítulo há uma introdução sobre acoplamentos transmitidos "espacialmente" (TS). Posteriormente, os valores de nJFN, cujo n4, são correlacionados com distância (dFN) e densidade eletrônica ao longo do caminho do acoplamento. No terceiro capítulo os mecanismos de transmissão da constante de acoplamento JFH em 2-F-benzaldeído foram investigados. A motivação para este estudo foi a observação do maior valor dessa constante em meio polar. Os resultados teóricos mostraram que a forma sinperiplanar é a mais estável, porém a porcentagem da forma antiperiplanar aumenta em solvente polar. Além disso, os resultados teóricos suportam um JFH maior para a forma anti. Esses resultados corroboram com o dado experimental acima mencionado. Seguindo a apresentação dos resultados, o capítulo 4 versa sobre o uso de constante de acoplamento vicinal (3JCH) para a determinação da estereoquímica de duplas ligações. Primeiro apresentamos a metodologia sel-HSQMBC-TOCSY utilizada para determinação do acoplamento 3JCH. Posteriormente apresentamos uma racionalização para os valores observados para derivados de quinolina e pirrolizidinonas, mostrando a importância da ocupância dos orbitais e da % de caráter s dos carbonos envolvidos para a transmissão desse acoplamento. Por fim, no capítulo 5 são apresentados os resultados para os experimentos de DOSY (Diffusion Ordered SpectroscopY). Neste capítulo apresentamos a sequência Oneshot-19F{1H} uma modificação da sequência original Oneshot-1H para detecção de 19F com desacoplamento de 1H / Abstract: The thesis "Study of the mechanisms of transmission of the scalar couplings through bond and/or through the electronic cloud close in space and studies of diffusion (DOSY) of 19F" is composed by 5 chapters. The first chapter is an overview of Nuclear Magnetic Resonance (NMR), pulse sequences to determine experimentally scalar spin-spin coupling constants (SSCC), mechanisms involved in the transmission of SSCC and Natural Bond Orbital analysis (NBO). The second chapter introduced the through space coupling constant (TS) transmission pathway. In addition, it was proposed a correlation among the values of nJFN, with n?4, the distance (dFN) and the electronic density along the coupling pathway. In the third chapter the mechanisms involved in the transmission of the JFH coupling constant in 2-F-benzaldehyde were investigated. The experimental observation of a higher coupling constant in polar solvent compared to the nonpolar one was our motivation to evaluate in details this coupling constant. It is important to highlight that was not possible to determine experimentally this coupling constant in nonpolar solvent because the value is smaller than spectral resolution. From theoretical calculation it was observed that the syn periplanar is the most stable conformer, however the population of the antiperiplanar conformer increases in polar solvent. Besides, the theoretical results support higher JFH value for the antiperiplanar conformer in comparison to syn periplanar. These results are in agreement with the experimental. Following the discussion, chapter 4 is related to the application of vicinal coupling constant (3JCH) for relatively stereochemical determination. The experimental 3JCH coupling was measured using sel-HSQMBC-TOCSY pulse sequence. In addition, it was done a rationalization of the couplings observed for quinolines and pirrozilidinones derivatives, suggesting that the % s character of the carbons and occupancy of the orbitals involved in the coupling pathway describes the experimental behavior. Finally, chapter 5 introduces the use of DOSY (Diffusion Ordered SpectroscopY). For this purpose, It was designed a pulse sequence dubbed Oneshot-19F{1H} ¿ consisting in a modification of the original Oneshot-1H to allow radiofrequency changes between 1H and 19F channels and a 1H decoupling during 19F acquisition / Doutorado / Quimica Organica / Doutora em Ciências

<p>Quantum chemical calculations have been performed to investigate radical cation rearrangement, radical carbonylation, and homolytic substitution reactions of organic molecules.</p><p>The rearrangement of the bicyclopropylidiene radical cation to the tetramethyleneethane radical cation is predicted to proceed with stepwise disrotatory opening of the two rings. Each ring opening is found to be combined with a striking pyramidalization of a carbon atom in the central bond.</p><p>The isomerization of the norbornadiene radical cation to the cycloheptatriene radical cation (<b>CHT</b><b>.+</b>), initialized by opening of a bridgehead–methylene bond, is investigated. The most favorable path involves concerted rearrangement to the norcaradiene radical cation followed by ring opening to <b>CHT</b><b>.+</b>. The barrier of this channel is found to be significantly reduced upon substitution of the methylene group with C(CH₃)₂.</p><p>Stepwise mechanisms are predicted to be favored over concerted isomerization for the McLafferty rearrangement of the radical cations of butanal and 3-fluorobutanal. The barrier for the concerted rearrangement is found to be lowered by 17.2 kcal/mol upon substitution, a result which is rationalized by the calculated dipole moments and atomic charges.</p><p>Recent experiments showed that photoinitiated carbonylation of alkyl iodides with [¹¹C]carbon monoxide may be significantly enhanced by using small amounts of ketones that have nπ* character of their excited triplet state. DFT calculations show the feasibility of an atom transfer type mechanism, proposed to explain these observations. Moreover, the computational results rationalize the observed differences in yield when using various alcohol solvents.</p><p>Finally, following photolysis of methyliodide, recent electron spin resonance spectroscopy experiments demonstrated that the S_H2 reaction ^•CD₃ + SiD₃CH₃ → CD₃SiD₃ + ^•CH₃ proceeds with high selectivity over the energetically more favorable D abstraction. The role of geometrical effects, especially the formation of prereactive complexes between methylsilane and methyliodide is studied, and a plausible explanation for the experimentally observed paradox is presented.</p>

A new family of oligonuclear cyano compounds incorporatingtransition (Pt) and main group (Tl) metals bound with anon-buttressed Pt-Tl bond was synthesised in aqueous solution.The metal-metal linkage is formed in the reaction betweenplatinum and thallium in their stable oxidation forms, Pt(II)and Tl(III), orvice versa: Pt(IV) and Tl(I). Four binuclear complexeswith a general composition [(CN)5Pt-Tl(CN)n(aq)]n-(n = 0-3) and a trinuclear species [(NC)5Pt-Tl-Pt(CN)5]3-were identified and structurally characterised insolution by multinuclear NMR, EXAFS and vibrationalspectroscopy. In aqueous solution the complexes exist inequilibrium. The distribution between the species can bealtered by varying the molar ratio Pt/Tl, cyanide concentrationand pH. Stability constants of the compounds weredetermined. A new compound (NC)5PtTl was also prepared in solid and its crystalstructure solved by a combination of X-ray powder diffractionand EXAFS. Altogether the values of195Pt-205Tl spin-spin coupling constants (25-71 kHz),interatomic Pt-Tl distances (2.598-2.638 Å), and vibrationstretching frequencies v (Pt-Tl) (159-164 cm-1) are fully indicative of a direct and unsupportedPt-Tl bond. The calculated values of Pt-Tl force constants(1.56-1.74 N· cm-1) are characteristic for single metal-metal bond.The oxidation status in the compounds can be viewed asintermediate between II and IV for platinum, and between I andIII for thallium, as reflected by the chemical shifts of195Pt and205Tl nuclei, C≡ N stretching frequencies andelectron binding energies. The compounds are capable to undergo a photoinducedtwo-electron transfer between the coupled hetero-metal ions.Upon irradiation into the metal-to-metal charge transferabsorption band, effective photoredox reaction takes place. Itresults in scission of the Pt-Tl bond and formation of variouscomplexes of oxidised platinum (Pt(III, IV)) and reducedthallium (Tl(I)). The values of photodecomposition quantumyields were determined from a stationary photolysis study ofthe heterometallic complexes. Nanosecond laser flash photolysisof the heteronuclear Pt-Tl cyano compounds was performed in thetimescale range 1· 10-6- 5· 10-2s and several intermediate species were detectedand characterised by optical spectroscopy. The heteronuclear Pt-Tl cyano compounds can be furthermodified in terms of their stability, solubility, and lightabsorption characteristics. It has been found that the platinumpentacyano unit of the [(NC)5Pt-Tl(CN)n(aq)]n-species is inert towards the tested ligands,whereas the thallium "part" of the complexes can be tunedsignificantly. A number of complexes [(NC)5Pt-Tl(L)m]x-(L-ligand) were prepared and characterised insolution. Compounds [(NC)5Pt-Tl(nta)(H2O)]3-, [(NC)5Pt-Tl(bipy)(DMSO)3], and [(NC)5Pt-Tl(bipy)2]have been prepared in solid and their structuresdetermined by single-crystal X-ray diffraction. <b>Keywords:</b>thallium, platinum, cyanide, metal-metal bond,non-buttressed, heterobimetallic, photoinduced, electrontransfer, redox reaction, NMR, chemical shift, spin-spincoupling constant, Raman, EXAFS, X-ray diffraction,equilibrium, oxidation state, oxidative addition,photolysis

<p>A new family of oligonuclear cyano compounds incorporatingtransition (Pt) and main group (Tl) metals bound with anon-buttressed Pt-Tl bond was synthesised in aqueous solution.The metal-metal linkage is formed in the reaction betweenplatinum and thallium in their stable oxidation forms, Pt(II)and Tl(III), or<i>vice versa</i>: Pt(IV) and Tl(I). Four binuclear complexeswith a general composition [(CN)₅Pt-Tl(CN)_n(aq)]^n-(n = 0-3) and a trinuclear species [(NC)₅Pt-Tl-Pt(CN)₅]^3-were identified and structurally characterised insolution by multinuclear NMR, EXAFS and vibrationalspectroscopy. In aqueous solution the complexes exist inequilibrium. The distribution between the species can bealtered by varying the molar ratio Pt/Tl, cyanide concentrationand pH. Stability constants of the compounds weredetermined.</p><p>A new compound (NC)₅PtTl was also prepared in solid and its crystalstructure solved by a combination of X-ray powder diffractionand EXAFS. Altogether the values of¹⁹⁵Pt-²⁰⁵Tl spin-spin coupling constants (25-71 kHz),interatomic Pt-Tl distances (2.598-2.638 Å), and vibrationstretching frequencies v (Pt-Tl) (159-164 cm^-1) are fully indicative of a direct and unsupportedPt-Tl bond. The calculated values of Pt-Tl force constants(1.56-1.74 N· cm^-1) are characteristic for single metal-metal bond.The oxidation status in the compounds can be viewed asintermediate between II and IV for platinum, and between I andIII for thallium, as reflected by the chemical shifts of¹⁹⁵Pt and²⁰⁵Tl nuclei, C≡ N stretching frequencies andelectron binding energies.</p><p>The compounds are capable to undergo a photoinducedtwo-electron transfer between the coupled hetero-metal ions.Upon irradiation into the metal-to-metal charge transferabsorption band, effective photoredox reaction takes place. Itresults in scission of the Pt-Tl bond and formation of variouscomplexes of oxidised platinum (Pt(III, IV)) and reducedthallium (Tl(I)). The values of photodecomposition quantumyields were determined from a stationary photolysis study ofthe heterometallic complexes. Nanosecond laser flash photolysisof the heteronuclear Pt-Tl cyano compounds was performed in thetimescale range 1· 10^-6- 5· 10^-2s and several intermediate species were detectedand characterised by optical spectroscopy.</p><p>The heteronuclear Pt-Tl cyano compounds can be furthermodified in terms of their stability, solubility, and lightabsorption characteristics. It has been found that the platinumpentacyano unit of the [(NC)₅Pt-Tl(CN)_n(aq)]^n-species is inert towards the tested ligands,whereas the thallium "part" of the complexes can be tunedsignificantly. A number of complexes [(NC)₅Pt-Tl(L)_m]^x-(L-ligand) were prepared and characterised insolution. Compounds [(NC)₅Pt-Tl(nta)(H₂O)]^3-, [(NC)₅Pt-Tl(bipy)(DMSO)₃], and [(NC)₅Pt-Tl(bipy)₂]have been prepared in solid and their structuresdetermined by single-crystal X-ray diffraction.</p><p><b>Keywords:</b>thallium, platinum, cyanide, metal-metal bond,non-buttressed, heterobimetallic, photoinduced, electrontransfer, redox reaction, NMR, chemical shift, spin-spincoupling constant, Raman, EXAFS, X-ray diffraction,equilibrium, oxidation state, oxidative addition,photolysis</p>

Quantum chemical calculations have been performed to investigate radical cation rearrangement, radical carbonylation, and homolytic substitution reactions of organic molecules. The rearrangement of the bicyclopropylidiene radical cation to the tetramethyleneethane radical cation is predicted to proceed with stepwise disrotatory opening of the two rings. Each ring opening is found to be combined with a striking pyramidalization of a carbon atom in the central bond. The isomerization of the norbornadiene radical cation to the cycloheptatriene radical cation (CHT.+), initialized by opening of a bridgehead–methylene bond, is investigated. The most favorable path involves concerted rearrangement to the norcaradiene radical cation followed by ring opening to CHT.+. The barrier of this channel is found to be significantly reduced upon substitution of the methylene group with C(CH3)2. Stepwise mechanisms are predicted to be favored over concerted isomerization for the McLafferty rearrangement of the radical cations of butanal and 3-fluorobutanal. The barrier for the concerted rearrangement is found to be lowered by 17.2 kcal/mol upon substitution, a result which is rationalized by the calculated dipole moments and atomic charges. Recent experiments showed that photoinitiated carbonylation of alkyl iodides with [11C]carbon monoxide may be significantly enhanced by using small amounts of ketones that have nπ* character of their excited triplet state. DFT calculations show the feasibility of an atom transfer type mechanism, proposed to explain these observations. Moreover, the computational results rationalize the observed differences in yield when using various alcohol solvents. Finally, following photolysis of methyliodide, recent electron spin resonance spectroscopy experiments demonstrated that the SH2 reaction •CD3 + SiD3CH3 → CD3SiD3 + •CH3 proceeds with high selectivity over the energetically more favorable D abstraction. The role of geometrical effects, especially the formation of prereactive complexes between methylsilane and methyliodide is studied, and a plausible explanation for the experimentally observed paradox is presented.

The cyclopentadienone-fused dihydropyrenes 46 and 47 were synthesized. The internal methyl resonances, the coupling constants, NICS calculations and X-ray results confirmed that the cyclopentadienone displays antiaromatic character resulting in bond localization in the annulene ring consistent with a 4n-pi fused system. The ring current of the dihydropyrene fragment is reduced by fusion of the antiaromatic system by about 80% of that caused by benzene. The syntheses of the methylfulvene fused dihydropyrene 56 and the phenylfulvene fused dihydropyrene 58 have been accomplished. The calculated and experimental NMR data and NICS calculations all demonstrated that the fulvenes had weak diatropic ring currents and caused bond localizations in the DHP rings, in which phenyl fulvene has a larger effect than that of methyl fulvene. A number of bis-dihydropyrene systems, bis-dihydropyrene ketone 117, bis-benzo[e]dihydropyrene ketone 119, benzo[e]dihydropyrene dihydropyrene ketone 122, bis-benzo[e]dihydropyrene methylene 124 and the benzo[e]dihydropyrene- dihydropyrene acetylene 130, have been synthesized, in which 117, 119 and 124 are homo-systems and 122 and 130 are hetero-systems. The multiple photoswitching properties study found that all of these systems except 130 showed multi-states during the photo opening and photo closing processes, which means that each end of the DHP units photo opens or closes separately rather than synchronously. In the homo switches 117, 119 and 124, the two DHP units act independently, but the relative differentiation is not very significant. On the other hand, the hetero-switch 122 showed fully differentiated photo opening process and almost a pure open-closed intermediate 122’ could be achieved. This is the first example which clearly showed four states in the UV closing process. The relative photo opening and closing rates compared to benzoDHP 36 have also been studied. It was found that while the carbonyl linker largely increased the relative photo opening rate (117, 119 and 122), the methylene linker only increased it slightly (124). The photo closing processes were always fast as usual. The studies of the thermal return reactions of these systems showed that while the carbonyl linker substantially slowed down the thermal return reactions of the DHP units (117, 119 and 122), the methylene linker speeded it up slightly (124). The mono-iron tricarbonyl benzo[e]dihydropyrene complex 152, the bis-iron tricarbonyl benzo[e]dihydropyrene complex 153 and the iron tetracarbonyl dihydropyrene complex 151 were synthesized. The structures of 152 and 153 were determined by X-ray crystallography. The coordinations of iron tricarbonyl moieties to the DHP rings caused a distortion of ca. 30 degree away from the central DHP plane. Coordination also increased bond alternation and reduced ring currents in the DHP rings. 1H-NMR and X-ray studies showed that 152 showed a weak paratropic ring current in the DHP ring. Iron coordination of the DHP completely stopped the photochromic properties of the dihydropyrenes.

The radiative &amp / #969 / &amp / #8594 / &amp / #960 / 0&amp / #960 / 0&amp / #947 / , &amp / #961 / &amp / #8594 / &amp / #960 / 0&amp / #960 / 0&amp / #947 / , &amp / #969 / &amp / #8594 / &amp / #960 / +&amp / #960 / &amp / #8722 / &amp / #947 / and &amp / #961 / &amp / #8594 / &amp / #960 / +&amp / #960 / &amp / #8722 / &amp / #947 / decays are studied by adding the effect of vector meson mixing to the amplitude of these decays. For the above decays we consider only &amp / #961 / &amp / #8722 / &amp / #969 / mixing. In addition to the &amp / #961 / &amp / #8722 / &amp / #969 / mixing, we also analyse the contributions coming from different intermediate states to examine the decay mechanism of these decays in a phenomenological framework. For &amp / #969 / &amp / #8594 / &amp / #960 / 0&amp / #960 / 0&amp / #947 / decay, we consider the contributions of the &amp / #961 / -meson and &amp / #963 / -meson intermediate states and of the kaon-loop, and for the &amp / #961 / &amp / #8594 / &amp / #960 / 0&amp / #960 / 0&amp / #947 / decay we calculate the amplitude using the contributions of the &amp / #969 / -meson and &amp / #963 / -meson intermediate states and pion-loop. Moreover, the radiative &amp / #969 / &amp / #8594 / &amp / #960 / +&amp / #960 / &amp / #8722 / &amp / #947 / decay is studied by considering the contributions of &amp / #963 / -meson and &amp / #961 / -meson intermediate states and the decay &amp / #961 / &amp / #8594 / &amp / #960 / +&amp / #960 / &amp / #8722 / &amp / #947 / is investigated by taking into account the contributions of bremmsstrahlung, pion-loop and &amp / #963 / - meson intermediate state amplitude. We also estimate the coupling constant g&amp / #969 / &amp / #963 / &amp / #947 / utilizing the latest experimental value of the branching ratio &amp / #969 / &amp / #8594 / &amp / #960 / 0&amp / #960 / 0&amp / #947 / .

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, foram calculados os fatores de forma e as constantes de acoplamento dos vértices mesônicos J/&#968; DsDs, J/&#968; Ds*Ds e J/&#968; Ds*Ds*usando a técnica das regras de soma da QCD (RSQCD) até a ordem 5 da OPE. Estes três vértices estão envolvidos em algumas das numerosas hipóteses que tentam explicar a estrutura interna de alguns mésons charmosos exóticos que começaram a ser observados a partir de 2003. Tais mésons não se encaixam no espectro do charmonium e/ou apresentam números quânticos exóticos dentro do modelo CQM (constituent quark model). Um exemplo é o méson Y(4140), cujo decaimento observado é no par J/&#968;&#966; enquanto o esperado seria que tivesse decaimento predominante em mésons com open charm, devido à sua massa. Uma das propostas para se entender este méson consiste em estudá-lo como um estado molecular Ds*ar{D}s*, de modo que seu decaimento seria Y(4140) &#8594; Ds* ar{D}s* &#8594; J/&#968;&#966;. Neste processo, aparecerão os vértices de interação estudados neste trabalho, de maneira que o conhecimento mais preciso de seus fatores de forma e de suas constantes de acoplamento pode beneficiar a compreensão sobre a constituição fundamental do Y(4140) assim como a de outros novos estados como o X(4350), Y(4274) e Y(4660) por exemplo. Foram considerados neste trabalho, todos os casos off-shell possíveis para cada um dos três vértices, obtendo assim dois fatores de forma distintos para o vértice J/&#968; DsDs, três para o vértice J/&#968; Ds*Ds e dois para o vértice J/&#968; Ds* Ds*. Nestes três vértices, os fatores de forma para o caso J/&#968; off-shell foram bem ajustados por curvas monopolares enquanto os casos Ds e Ds* foram ajustados por curvas exponenciais, o que está de acordo com o comportamento encontrado em trabalhos anteriores do grupo. Os cálculos das constantes de acoplamento tiveram como resultados: g_{J/&#968; Ds Ds} = 5.98^{+0.67}_{ -0.58}, g_{J/&#968; D*s Ds} = 4.30_{+0.41}^{-0.35}GeV^{-1} e g_{J/&#968; Ds* Ds*} = 7.47^{+1.04}_{-0.71}, resultados estes que estão compatíveis com os trabalhos anteriores que utilizaram as RSQCD para o cálculo das constantes de acoplamento dos vértices J/&#968; D(*)D(*). / In this work, the form factors and coupling constants of the meson vertices J/&#968; DsDs, J/&#968; Ds*Ds and J/&#968; Ds*Ds* have been calculated with the QCD sum rule (QCDSR) technique up to dimension 5 of the operator product expansion (OPE). These three vertices are involved in some of the numerous hypotheses that attempt to explain the internal structure of some exotic charmed mesons which began to be observed since 2003. Such mesons do not fit in the charmonium spectrum and/or have exotic quantum numbers within the CQM (constituent quark model). An example is the Y(4140) meson, which decays in the pair J/&#968;&#966; while the expected would be a dominant decay in open charm mesons. One of the proposals to understand this meson is to study it as a molecular state Ds*{D}s*, so it would decay as Y(4140)&#8594; Ds* {D}s* &#8594; J/&#968;&#966;.In this process, the vertices studied in this work will appear, so the more accurate knowledge of their form factors and their coupling constants can benefit our understanding of the fundamental constitution of the Y(4140) as well as other new states as the X(4350), Y(4274) and Y (4660) eg. In this study all possible off-shell cases for each of these three vertices were considered, thus obtaining two different form factors for the vertex J/&#968; DsDs, three for the vertex J/&#968; Ds*Ds and two for the vertex J/&#968; Ds* Ds*. In these three vertices, the form factors for the J/&#968; off-shell case were well fitted by monopolar curves, while the Ds and Ds* off-shell cases were well fitted by exponential curves which is in agreement with the behavior found in previous work of the group. The calculations of the coupling constants leaded to the following results: g_{J/&#968; Ds Ds} = 5.98^{+0.67}_{-0.58}, g_{J/&#968; Ds* Ds} = 4.30^{+0.41}_{-0.35}GeV^{-1} and g_{J/&#968; Ds* Ds*} = 7.47^{+1.04}_{-0.71}, these results are compatible with previous QCDSR works for the non strange vertices J/&#968;D(*)D(*).

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, foram calculados os fatores de forma e as constantes de acoplamento dos vértices mesônicos J/&#968; DsDs, J/&#968; Ds*Ds e J/&#968; Ds*Ds*usando a técnica das regras de soma da QCD (RSQCD) até a ordem 5 da OPE. Estes três vértices estão envolvidos em algumas das numerosas hipóteses que tentam explicar a estrutura interna de alguns mésons charmosos exóticos que começaram a ser observados a partir de 2003. Tais mésons não se encaixam no espectro do charmonium e/ou apresentam números quânticos exóticos dentro do modelo CQM (constituent quark model). Um exemplo é o méson Y(4140), cujo decaimento observado é no par J/&#968;&#966; enquanto o esperado seria que tivesse decaimento predominante em mésons com open charm, devido à sua massa. Uma das propostas para se entender este méson consiste em estudá-lo como um estado molecular Ds*ar{D}s*, de modo que seu decaimento seria Y(4140) &#8594; Ds* ar{D}s* &#8594; J/&#968;&#966;. Neste processo, aparecerão os vértices de interação estudados neste trabalho, de maneira que o conhecimento mais preciso de seus fatores de forma e de suas constantes de acoplamento pode beneficiar a compreensão sobre a constituição fundamental do Y(4140) assim como a de outros novos estados como o X(4350), Y(4274) e Y(4660) por exemplo. Foram considerados neste trabalho, todos os casos off-shell possíveis para cada um dos três vértices, obtendo assim dois fatores de forma distintos para o vértice J/&#968; DsDs, três para o vértice J/&#968; Ds*Ds e dois para o vértice J/&#968; Ds* Ds*. Nestes três vértices, os fatores de forma para o caso J/&#968; off-shell foram bem ajustados por curvas monopolares enquanto os casos Ds e Ds* foram ajustados por curvas exponenciais, o que está de acordo com o comportamento encontrado em trabalhos anteriores do grupo. Os cálculos das constantes de acoplamento tiveram como resultados: g_{J/&#968; Ds Ds} = 5.98^{+0.67}_{ -0.58}, g_{J/&#968; D*s Ds} = 4.30_{+0.41}^{-0.35}GeV^{-1} e g_{J/&#968; Ds* Ds*} = 7.47^{+1.04}_{-0.71}, resultados estes que estão compatíveis com os trabalhos anteriores que utilizaram as RSQCD para o cálculo das constantes de acoplamento dos vértices J/&#968; D(*)D(*). / In this work, the form factors and coupling constants of the meson vertices J/&#968; DsDs, J/&#968; Ds*Ds and J/&#968; Ds*Ds* have been calculated with the QCD sum rule (QCDSR) technique up to dimension 5 of the operator product expansion (OPE). These three vertices are involved in some of the numerous hypotheses that attempt to explain the internal structure of some exotic charmed mesons which began to be observed since 2003. Such mesons do not fit in the charmonium spectrum and/or have exotic quantum numbers within the CQM (constituent quark model). An example is the Y(4140) meson, which decays in the pair J/&#968;&#966; while the expected would be a dominant decay in open charm mesons. One of the proposals to understand this meson is to study it as a molecular state Ds*{D}s*, so it would decay as Y(4140)&#8594; Ds* {D}s* &#8594; J/&#968;&#966;.In this process, the vertices studied in this work will appear, so the more accurate knowledge of their form factors and their coupling constants can benefit our understanding of the fundamental constitution of the Y(4140) as well as other new states as the X(4350), Y(4274) and Y (4660) eg. In this study all possible off-shell cases for each of these three vertices were considered, thus obtaining two different form factors for the vertex J/&#968; DsDs, three for the vertex J/&#968; Ds*Ds and two for the vertex J/&#968; Ds* Ds*. In these three vertices, the form factors for the J/&#968; off-shell case were well fitted by monopolar curves, while the Ds and Ds* off-shell cases were well fitted by exponential curves which is in agreement with the behavior found in previous work of the group. The calculations of the coupling constants leaded to the following results: g_{J/&#968; Ds Ds} = 5.98^{+0.67}_{-0.58}, g_{J/&#968; Ds* Ds} = 4.30^{+0.41}_{-0.35}GeV^{-1} and g_{J/&#968; Ds* Ds*} = 7.47^{+1.04}_{-0.71}, these results are compatible with previous QCDSR works for the non strange vertices J/&#968;D(*)D(*).

Cette thèse traite de certaines propriétés spectrales de deux classes spécifiques des opérateurs périodiques. Nous nous intéressons tout d’abord à un modèle périodique perturbée par un opérateur dépendant d’un petit paramètre semi-classique. Nous obtenons alors le comportement asymptotique de la fonction du comptage des valeurs propres dans les gaps spectrales avec une estimation optimale du reste. Le second modèle étudié dans cette thèse est un modèle elliptique périodique d’ordre deux perturbée par un opérateur dépendant d’une grande constante de couplage. Nous donnons également la description de la fonction de compactage des valeurs propres lorsque la constante de couplage tend vers l’infini. La dernière partie de cette thèse discute l’étude du spectre discret de l’opérateur de Schrödinger avec un potentiel très oscillent dépendant d’un petit paramètre semi-classique. / This Ph.D thesis deals with some spectral properties of two specific classes of two periodic operators. We are firstly interested in the model periodic perturbed by operator depending on a small semi-classical constant. We obtain an asymptotic behavior of the eigenvalue counting function in the spectral gaps with scharp remainder estimate. The second model studied in this thesis is a two-dimensional periodic elliptic second order opera-tor perturbed by operator depending on a large coupling constant. We also give the description of the counting function of eigenvalues when the coupling constant tends to infinity. The last part of this thesis highlights the study the spectrum of a Schrödinger operator perturbed by a fast oscillatingdecaying potential depending on a small parameter.