Les travaux théoriques réalisés dans le cadre de la thèse nous ont permis d'étudier en détail, sur la base de méthodes DFT, TD-DFT et ab initio les propriétés structurales, électroniques et spectroscopiques de deux classes de molécules, les composés carbonyles hydrures des métaux de transition de la 1re et 3me rangée (Mn, Re) et les complexes cyclométalants phenyl pyridine de l'iridium. L'accent a été mis plus particulièrement sur les effets de couplage spin-orbite sur les spectres d'absorption électronique de ces molécules. La quantification de ces effets a permis de montrer que seuls les spectres électroniques des complexes possédant un centre métallique de la 3me rangée des métaux de transition (Re, Ir) étaient modifiés par la correction spin-orbite en perturbation. Le caractère des états, MC ou MLCT, la proximité des états singulets et triplets sont les facteurs qui influencent fortement l'interaction spinorbite entre états excités. Un effet remarquable observé pour le complexe du rhenium est le décalage important du spectre d'absorption vers le rouge du à l'éclatement de l'état triplet le plus bas. Dans ce cas l'effet de couplage spinorbite doit être pris en compte pour obtenir un spectre plus proche de l'expérience. Un effet spin-orbite déjà observé sur d'autres systèmes est l'augmentation de de la densité d'états par éclatement des états triplets et la diminuation des force d'oscillateur qui se répartissent sur ces états pour aboutir à des spectres d'absorption électronique plus étendus et moins intenses. L'étude menée sur les complexes d'iridium pour lesquels les spectres expérimentaux sont particulièrement mal résolus, montre un accord remarquable entre ceux-ci est les spectres d'absorption théoriques TD-DFT. Cependant les effets de fonctionnelle peuvent jouer un rôle important sur la qualité des spectres. Pour ces molécules les calculs ab initio n'ont pu aboutir au-delà du niveau CASSCF. Les états excités sont très délocalisés dans ces molécules et il est difficile de décrire au même niveau d'approximation les différents types d'états MLCT, LLCT, MC, LMCT... Dans la plupart des cas les fonctionnelles B3LYP et PW91 donnent des résultats satisfaisants pour les complexes d'iridium. Les éclatements spin-orbite des états électroniques triplets peuvent être supérieurs à 1500 cm-1 dans les complexes possédant un centre métallique de la 3me rangée des métaux de transition.

Les cristaux moléculaires présentent des applications importantes dans l'électronique/l'optoélectronique, les systèmes 'host-guest', ou encore pour des systèmes mécaniques photo-actifs.Les propriétés mentionnées ci-dessus sont sensiblement affectées par le polymorphisme, qui influence le comportement de chaque composé présent dans une forme cristalline définie. Ce phénomène est rendu difficile à étudier de par la présence d'interactions de dispersion et/ou liaisons hydrogène.Avec l'objectif de décrire précisément ces interactions, et pour prédire des propriétés électroniques, une approche de mécanique quantique (QM) a été adoptée, utilisant la Théorie de la Fonctionnelle de la Densité (DFT).Les avancements les plus importants dans l'étude des cristaux examinées, sont: i) une prédiction correcte de la stabilité relative entre olymorphes, similaire aux résultats prévus par des méthodes plus coûteuses, peut être obtenue par l'utilisation d'une ombinaison entre la DFT et des corrections semi-empiriques moins coûteuses; ii) Le benchmark réalisé ici peut être utile dans le cadre de la création de nouveaux corrections pour la dispersion en DFT; iii) la rédiction de la structure de quatre formes cristallines d'un composé 'host-guest' précédemment synthétisé a été réalisée, notamment grâce aux calculs des déplacements chimiques (RMN) ayant permis de compléter et corriger l'interprétation RMN des résultats expérimentaux; iv) un protocole calculatoire pour l'étude des procédés photophysiques et photochimiques d'un cristal moléculaire thermochromique a été mis en place, basé sur la caractérisation des clusters de molécules extraits du cristal 'bulk' par la mécanique quantique. / Molecular crystals find relevant applications in electronics/optoelectronics, host-guest systems, or photo-activated mechanical systems. The properties mentioned above are severely affected by polymorphism, which influences the behaviour of each compound in a definite crystalline form. This is complicated by the dispersion and/or hydrogen bond interactions, which govern the molecular displacement within the solid. In order to describe accurately these interactions, and to predict advanced electronic properties, a quantum (QM) computational approach has been adopted, at the Density Functional Theory (DFT) level. The more notable advancements in the characterization of the studied crystals are: i) the demonstration that a wise combination of DFT and costless semiempirical corrections for dispersion leads to predict accurately the relative stability between polymorphs, almost at the same level of higher and costly methods; ii) The benchmarking carried out against these last can be exploited to design new dispersion-correction schemes for DFT iii) the structural prediction of four crystal forms of a solid host-guest compound previously synthetized, for that we addressed and clarified some lacks on the experimental NMR interpretation, through calculated NMR chemical shifts; iv) the optimization of a computational protocol for the study of the photophysical-photochemical processes of a thermochromic molecular crystal – based on the QM characterization of clusters of molecules extracted from the bulk crystal.

Ces travaux de thèse se sont concentrés sur le développement, l'implémentation et l'application de différents types de méthodes quantiques prenant la corrélation électronique en compte, dans le but de fournir des outils performants pour la description de systèmes moléculaires à l'état fondamental et excité. La méthode dite DMRG (Density Matrix Renormalization Group) a été étudiée et un logiciel correspondant a été développé en FORTRAN. Cette méthode permet de limiter le nombre d'états électroniques à prendre en compte, ce qui fait gagner du temps de calcul, tout en assurant une précision des résultats du même ordre que celle fournie par les toutes meilleures méthodes post-Hartree-Fock actuelles. Dans la deuxième partie de cette thèse, nous avons utilisé une autre méthode : la DFT (Density Functional Theory). Une étude théorique a été effectuée sur deux fonctionnelles à séparation de portée (HISS-A et -B) afin d'évaluer dans quelle mesure ces fonctionnelles, développées au départ pour l'étude des systèmes métalliques, pouvaient être appliquées à la description de l'état fondamental et excité de systèmes moléculaires hautement conjugués. Nous avons également utilisé la DFT afin de modéliser et rationaliser le comportement photo-physique d'un composé moléculaire présentant une émission dite " duale ". Nous avons pu ainsi caractériser le comportement complexe de la molécule à l'état excité et expliquer les résultats surprenants qui avaient été observés, en particulier au niveau des spectres d'émission UV et d'excitation de fluorescence. Le phénomène d'émission duale observé a ainsi pu être lié à la présence d'un degré de liberté conformationnel important de la molécule. / In the last few years, a lot of energy has been put forward in the area of quantum chemistry to develop new methods, or to improve existing methods, that are able to describe very precisely the electronic structure of molecular systems. In this manuscript, a precise overview of such a method (namely the Density Matrix Renormalization Group, DMRG method) is given. A software able to carry out DMRG calculations has indeed been developed from scratch in the laboratory during this thesis. This method can be seen as a post-Hartree-Fock method, in which only the electronic states that are relevant for the correct description of the molecule are kept. In this way, the computational cost remains acceptable, and the results are in line with those given by "exact" methods such as full-CI. Density Functional Theory (DFT) has also been investigated in this work. DFT and TD-DFT calculations have indeed also been carried out. The performances of two middle-range-separated functionals, namely HISS-A and HISS-B, to describe electronic transitions in conjugated molecules have been probed in a theory vs. theory study. Those functionals, which had been first developed for the study of metals, show to be adequate for the correct description of electronic excitations of chromophores and of push-pull molecules. Optical properties of a dual emittor have also been studied using TD-DFT. The dual emission of this molecule has been shown to stem from the presence of two distinct emissive states, respectively of Intramolecular Charge Transfer (ICT) and locally excited (LE) nature. TD-DFT has allowed us to link those two emissive states to two different conformations of the molecule.

No description available.

Light-harvesting compounds are developed for a variety of purposes pertaining to areas such as energy-capture, chemical transformations, and lighting. There is a need to better understand the reactivity and excited state properties of these compounds. Many experiments focus on gleaning information about reactivity by observing spectral changes over time intervals ranging from femtoseconds to minutes (IR, UV-VIS, and UV-VIS pump-probe spectroscopy). This dissertation focuses on the interpretation of the experimental data from a computational perspective and methodological studies to determine reasonable levels of theory for each system. Three vignettes of this approach will be discussed. First, a mononuclear tungsten complex was found to be capable of self-sensitized catalytic H2 production. Experimental mechanistic studies employed time-resolved IR spectroscopy to capture spectral signatures of potential catalytic intermediates. DFT computational methods were utilized to predict geometries, energies, and harmonic stretching frequencies of a variety of catalytic intermediates that correlate rather well with experiment. For studying the excited state, the prototypical system that is both well-known and well-behaved is the [Ru(bpy)3]2+ ion. This complex undergoes a MLCT excitation and ultimately forms a long-lived 3MLCT state with a lifetime on the order of µs. While several computational studies exist, a systematic study on what dictates an appropriate level of theory for correctly describing this system is absent from the literature. We conduct a systematic study of a series of DFT functionals and basis set combinations to evaluate the relative energies of the MLCT and MC states, as well as correctly predicting the character of excitations observed in the transient UV-VIS spectra of the MLCT excited state. Finally, the absorption and emission spectra of a series of polycyclic aromatic azaborines were simulated and compared to their experimental values. Experimentally, some compounds exhibit large, solvent-dependent Stokes shifts consistent with CT excitations. Unfortunately, the excited state chemistry is not so straightforward and some of these compounds may become deprotonated in the ES, thus resulting in a charge-separated state. As a by-product of this project, the results from each method suggest that, contrary to literature precedent, typical hybrid functionals appear to overestimate the CT character of the computed excitations.

Une étude théorique basée sur la théorie de la fonctionnelle de la densité (DFT) a été réalisée sur un ensemble de complexes organométalliques mono, di et trinucléaires à base de fer, de ruthénium ou de platine. Les résultats obtenus sur les complexes mononucléaires à base de fer révèlent que la longueur du chaînon π de carbone n'a qu'une influence mineure sur les propriétés électroniques mais affectent les propriétés spectroscopiques. Une étude entreprise sur des systèmes contenant un ligand aromatique polycyclique a montré que la présence de molécules de solvant coordonnant abaisse les barrières énergétiques et par conséquence, facilite le réarrangement haptotropique du greffon organoruthénium sur le ligand organique. L'étude théorique réalisée sur des nouveaux systèmes de type [2]rotaxane a révélé que la longueur du chaînon π du fil moléculaire enfilé au travers d'un macrocycle influence les énergies d'interaction non covalente dans ces systèmes. Il a été montré que ces interactions non covalentes sont principalement dues à des liaisons hydrogène formées entre le macrocycle et le fil moléculaire. / A theoretical study based on density functional theory (DFT) was performed on several series of organometallic mono, bi and trinuclear iron, ruthenium and platinum based complexes. The results on mononuclear iron based complexes indicate that the length of the π carbon bridge in these systems has only a minor influence on the electronic properties but affect somewhat the spectroscopic properties. A study was conducted on systems containing polycyclic aromatic ligand showing that the presence of a coordinating solvent molecule in the viscinity of the metal atom bound on top of the polycycle strongly lowers the energy barriers and consequently facilitates the haptotropic rearrangement of the grafted organoruthenium entity. The theoretical study of new systems of [2]rotaxane type has revealed that the length of the π bridge of the molecular wire threaded in a macrocycle influences the weak noncovalent interaction energies in these systems. It has been shown that these noncovalent interactions are mainly due to hydrogen bonds formed between the macrocycle and the threaded molecular wire.

This work tries to show the significant competence and functionality of density functional theory (DFT) and time-dependent density functional theory (TD-DFT) as theoretical approaches, supporting experimental measurements in various fields of physics from astrophysics to surface science, to study the electronic structure and spectroscopic properties of molecules and clusters: Silicon nanocrystals: Due to their optical properties, silicon nanocrystals have attracted considerable attention in astrophysics. In this work, the optical properties of H-passivated silicon nanocrystals are determined by the energetics of the frontier orbitals and their dependence on the deformation in the relaxed excited state, using DFT and TD-DFT. The Jahn-Teller effect in the lowest excited state results in a distortion toward tetragonal symmetry, contributing significantly to the red shift of the photoluminescence (PL) spectra. Therefore, the deformation in the relaxed excited state consists of a symmetry conserving part and of a symmetry-breaking distortion from Td toward D2d. For nanocrystals up to a diameter of 1.5 nm, we project the deformations at the minima of the excited state potential surface onto the different symmetries, allowing for a discrimination of the respective contributions to the total Stokes shift. The results show a quantitative agreement between the TD-DFT calculations of PL gap and the observed PL energies better than 0.2 eV. It is also seen that the large PL linewidth is the fundamental property of each cluster, not of ensemble average over clusters of different size. 2,3-Benzofluorene: We have presented new theoretical results on the absorption spectroscopy of 2,3-benzofluorene (Bzf) for the transition from the ground state, S0, to the first electronically excited singlet state, S1, to support the measurements of S1(1A´) <- S0(1A´) absorption spectrum of jet-cooled Bzf. The potential energy surfaces (PESs) of the S(n=0,1,2) states of Bzf have been investigated with calculations based on DFT and TD-DFT. At the B3LYP/TZ level of theory, TD-DFT does not deliver a realistic difference between the excited S1 and S2 potential energy surfaces, a problem which can be avoided by introducing a reference geometry (q*) where this difference coincides with the observation. In this geometry, an expression for the Herzberg-Teller corrected intensities of the vibronic bands is proposed, allowing a straightforward assignment of the observed a′ modes below 900 cm−1, including realistic calculated intensities. In spite of the difficulties caused by the small energy difference between the S1 and S2 states, we have obtained a reasonable theoretical absorption spectrum based on a TD-DFT approach applied to the slightly modified molecular geometry. Although the agreement between the theoretical and observed spectra is very good only for vibrational modes with frequencies lower than 900 cm−1, we consider our calculations to be the best approach to an ab initio study realized for Bzf until now since only parametrized force fields had been used before. (Ni–, Pd–, Pt–) Phthalocyanine: We studied the HOMO–LUMO gap shrinking in order to investigate the tip-induced polarization in scanning tunneling spectroscopy (STS) of d8 (Ni, Pd, and Pt) phthalocyanines. By means of DFT, the electronic structure and vibronic properties of single neutral NiPc, PdPc, and PtPc and their singly and doubly ionized cations and anions have been calculated. Interestingly, the position of the HOMO decreases systematically with increasing the atomic number of the central metal atom. The first ionization energies of neutral molecules increase by changing the central metal atom, while the electron affinities remain constant. This causes an increase in the HOMO–LUMO gap. These results show a clear correlation to experimental observations. Furthermore, partitioning of the reorganization energy, corresponding to the photoelectron spectra of the first and second ionizations of studied molecules, into normal mode contributions shows that the major contributions are due to several vibrational modes with a1g symmetry and energies lower than 1600 cm−1. The results reveal that the reorganization energy due to the singly positive ionization in the studied molecules is about one order of magnitude less than other reorganization energies, which makes these metal–phthalocyanines more attractive as electron donor for intramolecular electron transfer in electron acceptor–donor systems.

Les précurseurs de ligands base de Schiff électro-donneurs et électro-accepteurs R-ONOH₂ sont préparés par réaction de monocondensation entre les β-dicétones appropriées et respectivement le 1,2- et le 1,2-4-nitro-aminophénol. Ils existent exclusivement sous leurs formes tautomériques céto-énamine en solution et à l'état solide. Dans les complexes correspondants de NiII et de CuII, le métal adopte une géométrie plan carré et est coordiné par les atomes d'azote et d'oxygène du ligand dianionique tridentate et par l'azote du coligand pyridine. L'hyperpolarisabilité quadratique, déterminée par la technique DHL est très élevée. La substitution de la pyridine par la 4,4'-bipyridine conduit systématiquement aux complexes dimériques correspondants. Un composé similaire comportant l'espaceur bis(4-pyridyle)acétylène est formé après réaction de couplage croisé de Sonogashira. Cette même réaction de couplage croisé entre les blocs de construction électrodonneurs et électro-accepteur permettent de préparer le système «push-pull» D-π-A désiré. Les réponses ONL du second ordre des complexes contenant le ligand électro-actif methylène-pyrane peuvent être modulées par bi- (R = An) et tétra- (R = Fc) oxydation réversible avec formation/rupture d'une liaison C-C, constituant ainsi un nouvel exemple de commutateur ONL-2 réversible. / Electron donating and electron withdrawing ligand precursors R-ONOH₂ were prepared by monocondensation reaction of the appropriate β-diketones and 1,2- and 1,2-4-nitro-aminophenol, respectively. They do exclusively exist as their enaminone tautomeric form both in solid-state and in solution phase. In their corresponding Schiff base complexes of NiII and CuII, the central metal is tetracoordinated in a square-planar environment. The coordination sphere is formed by the nitrogen and oxygen atoms of the dianionic tridentate ligand and the fourth coordination site is occupied by the nitrogen atom of the pyridine co-ligand. The derivative exhibited a high quadratic hyperpolarizability (β1.91) determined by the HLS technique. Substitution of 4,4’-bipyridine for pyridine invariably leads to the formation of the respective dimers [(R-ONO)MII(4,4’-bipy)MII(ONO-R)]. A similar compound having the bis(4-pyridyle)acetylene as spacer was formed upon cross-coupling Sonogashira reaction with ethynylpyridine chlorhydrate. The same cross-coupling reaction carried out between the electron releasing and electron withdrawing building blocks, respectively, allowed the preparation of the expected «push-pull» D-π-A system. The second-order NLO responses of compounds bearing a redox active methylenepyran ligand can be modulated upon reversible bi- (R = An) and tetra- (R = Fc) oxydation involving C-C bond formation/breaking reactions, thus forming a new class of NLO molecular switches.

<p>U ovoj doktorskoj disertaciji je radi fizičko-hemijske karakterizacije i ispitivanja potencijalne<br />biolo&scaron;ke aktivnosti sintetisano&nbsp; 40&nbsp; derivata mono(tio)karbohidrazona. Strukture dobijenih jedinjenja su potvrđene&nbsp; NMR&nbsp; i&nbsp; FT&ndash;IR&nbsp; spektroskopijom,&nbsp; elementalnom&nbsp; i&nbsp; rendgenskom&nbsp; strukturnom&nbsp; analizom. Uticaj&nbsp; rastvarača&nbsp; i&nbsp; prisutnog&nbsp; supstituenta&nbsp; na&nbsp; položaje apsorpcionih&nbsp; maksimuma&nbsp; ispitani&nbsp; su&nbsp; po principima LSER i LFER metoda. Teorijski proračuni za sintetisana jedinjenja izvedeni su&nbsp; primenom TD&ndash;DFT&nbsp; metode.&nbsp; Jonizacione&nbsp; konstante&nbsp; derivata&nbsp; mono(tio)karbohidrazona&nbsp; su&nbsp; određene potenciometrijskim&nbsp; titracijama.&nbsp; Antioksidativna&nbsp; aktivnost&nbsp; je&nbsp; određena&nbsp; primenom&nbsp; tri&nbsp; testa:&nbsp; DPPH, ABTS&nbsp; i&nbsp; FRAP&nbsp; testa.&nbsp; Antimikrobna&nbsp; aktivnost&nbsp; je&nbsp; ispitana&nbsp; mikrodilucionom&nbsp; metodom&nbsp; na&nbsp; dva&nbsp; soja bakterija:&nbsp; Staphylococcus&nbsp; aureus&nbsp; i&nbsp; Escherichia&nbsp; coli.&nbsp; Za&nbsp; jedinjenja&nbsp; koja&nbsp; su&nbsp; pokazali&nbsp; antimikrobnu aktivnost je&nbsp; ispitan procenat citotoksičnosti.&nbsp; Sveukupan&nbsp; zaključak o sličnosti i razlikama sintetisanih derivata izveden je na osnovu multivarijatnih metoda klaster analize i analize glavnih komponenti.</p> / <p>In this doctoral dissertation, 40 mono(thio)carbohydrazone derivatives were synthesized for the purpose of physico-chemical characterization and examination of potential biological activity. The structures of the obtained compounds were confirmed by NMR and FT &ndash;IR spectroscopy, elemental analysis&nbsp; and&nbsp; X-ray&nbsp; structural&nbsp; analysis.&nbsp; The&nbsp; influence&nbsp; of&nbsp; solvent&nbsp; and&nbsp; substituent&nbsp; present&nbsp; on&nbsp; the positions&nbsp; of&nbsp; absorption maxima&nbsp; was&nbsp; examined&nbsp; according&nbsp; to&nbsp; the&nbsp; principles&nbsp; of&nbsp; LSER&nbsp; and&nbsp; LFER methods.&nbsp; Theoretical&nbsp; calculations&nbsp; for&nbsp; the&nbsp; synthesized&nbsp; compounds&nbsp; were&nbsp; performed&nbsp; by&nbsp; the&nbsp; TD&ndash;DFT method.&nbsp; The&nbsp; acid&nbsp; constants&nbsp; of&nbsp; mono(thio)carbohydrazone&nbsp; derivatives&nbsp; were&nbsp; determined&nbsp; by potentiometric&nbsp; titrations.&nbsp; Antioxidant&nbsp; activity&nbsp; was&nbsp; determined&nbsp; using&nbsp; three&nbsp; tests:&nbsp; DPPH,&nbsp; ABTS&nbsp; and FRAP test. Antimicrobial activity was examined by microdilution method on two strains of bacteria: Staphylococcus&nbsp; aureus&nbsp; and&nbsp; Escherichia&nbsp; coli.&nbsp; The&nbsp; percentage&nbsp; of&nbsp; cytotoxicity&nbsp; was&nbsp; examined&nbsp; for compounds&nbsp; that&nbsp; showed&nbsp; antimicrobial&nbsp; activity.&nbsp; Overall&nbsp; conclusion&nbsp; about&nbsp; the&nbsp; similarities&nbsp; and differences of the synthesized&nbsp; derivatives was studied by multivariate&nbsp; methods of cluster analysis and analysis of principal components.</p>

<p>This thesis presents and uses the techniques of computational chemistry to explore two different processes induced in human skin by ultraviolet light. The first is the transformation of urocanic acid into a immunosuppressing agent, and the other is the enzymatic action of the 8-oxoguanine glycosylase enzyme. </p><p>The photochemistry of urocanic acid is investigated by time-dependent density functional theory. Vertical absorption spectra of the molecule in different forms and environments is assigned and candidate states for the photochemistry at different wavelengths are identified. </p><p>Molecular dynamics simulations of urocanic acid in gas phase and aqueous solution reveals considerable flexibility under experimental conditions, particularly for for the <i>cis</i> isomer where competition between intra- and inter-molecular interactions increases flexibility. </p><p>A model to explain the observed gas phase photochemistry of urocanic acid is developed and it is shown that a reinterpretation in terms of a mixture between isomers significantly enhances the agreement between theory and experiment , and resolves several peculiarities in the spectrum. </p><p>A model for the photochemistry in the aqueous phase of urocanic acid is then developed, in which two excited states governs the efficiency of photoisomerization. The point of entrance into a conical intersection seam is shown to explain the wavelength dependence of photoisomerization quantum yield. </p><p>Finally some mechanistic aspects of the DNA repair enzyme 8-oxoguanine glycosylase is investigated with density functional theory. It is found that the critical amino acid of the active site can provide catalytic power in several different manners, and that a recent proposal involving a S<i>N</i>1 type of mechanism seems the most efficient one.</p>