This mémoire presents my current research interests in micro and nano-mechanics in a comprehensive manuscript. Our experimental device is first presented: this atomic force microscope, designed and realized in the Laboratoire de Physique de l'ENS Lyon, is based on a quadrature phase differential interferometer. It features a very high resolution (down to 10 fm/rtHz) in the measurement of deflexion, down to low frequencies and on a huge input range. The dual output of the interferometer implies a specific handling to interface common scanning probe microscope controllers. We developed analog circuitries to tackle static (contact mode) and dynamic (tapping mode) operations, and we demonstrate their performance by imaging a simple calibration sample. As a first application, we used the high sensitivity of our interferometer to study the mechanical behavior of micro-cantilevers from their fluctuations. The keystone of the analysis is the Fluctuation-Dissipation Theorem (FDT), relating the thermal noise spectrum to the dissipative part of the response. We apply this strategy to confront Sader's model for viscous dissipation with measurements on raw silicon cantilevers in air, demonstrating an excellent agreement. When a gold coating is added, the thermal noise is strongly modified, presenting a 1/f like trend at low frequencies: we show that this behavior is due to a viscoelastic damping, and we provide a quantitative phenomenological model. We also characterize the mechanical properties of cantilevers (stiffness and Elastic Moduli) from a mapping of the thermal noise on their surface. This analysis validates the description of the system in term of its normal modes of oscillations in an Euler-Bernoulli framework for flexion and in Saint-Venant approach for torsion, but points toward a refined model for the dispersion relation of torsional modes. Finally, we present peeling experiments on a single wall carbon nanotube attached to the cantilever tip. It is pushed against a flat substrate, and we measure the quasi-static force as well as the dynamic stiffness using an analysis of the thermal noise during this process. The most striking feature of these two observables is a plateau curve for a large range of compression, the values of which are substrate dependent. We use the Elastica to describe the shape of the nanotube, and a simple energy of adhesion per unit length Ea to describe the interaction with the substrate. We analytically derive a complete description of the expected behavior in the limit of long nanotubes. The analysis of the experimental data within this simple framework naturally leads to every quantity of interest in the problem: the force plateau is a direct measurement of the energy of adhesion Ea for each substrate, and we easily determine the mechanical properties of the nanotube itself.

Cette thèse a pour objet l'étude du transport électronique dans les nanotubes de carbone monoparois par l'intermédiaire des fluctuations du courant. L'étude se place dans le cadre de la physique mésoscopique dans des conducteurs balistiques. Dans ce type de conducteur, plusieurs régimes diff´erents peuvent apparaître : blocage de Coulomb, transport modulé par les interférences quantiques, effet Kondo. Nous avons étudié les fluctuations du courant dans un régime d'interféromètre de type Fabry-Pérot électronique qui se présente comme une situation id´eale afin de sonder le régime où l'effet des interactions est faible. Les fluctuations du courant ont été analysées dans le formalisme de Landauer-Büttiker et nous obtenons une bonne correspondance entre la théorie et l'expérience. Nous avons ainsi observé la suppression du bruit dans les régimes de transmission unitaire et, par le biais des données combinées de la conductance et du bruit, nous avons pu déterminer les transmissions pour des canaux de conduction non dégénérés. Par ailleurs, le régime de l'effet Kondo a fait l'objet d'une étude dans laquelle nous avons observé des comportements universels dans la conductance et le bruit. Nous avons ajusté ces différentes grandeurs avec une théorie de bosons esclaves de champ moyen. Finalement, nous avons étudié une configuration de type Hanbury Brown et Twiss : un nanotube monoparoi sur lequel nous avons déposé un multiparoi qui nous sert de sonde afin d'injecter des électrons sur le conducteur.

Kohlenstoffnanoröhrchen (engl. carbon nanotube, CNT) sind vielversprechende Kandidaten für den Ersatz von Kupferleitbahnen die bei weiterer Strukturverkleinerung von integrierten Schaltkreisen notwendig wird. In dieser Arbeit wird mit Hilfe von ab-initio Simulationen auf Basis der Dichtefunktionaltheorie die elektronische Struktur von halbleitenden CNTs beispielhaft anhand des (8,4)-CNTs untersucht. Nach Besetzung des CNT mit Metallatomen, hier Kobalt, zeigen sich massive Änderungen der Bandstruktur. Es reichen bereits überraschend kleine Mengen des Metalls aus, um einen starken Effekt zu erreichen. Die Änderungen der elektronischen Struktur sind stark abhängig von der genauen Position der Metallatome relativ zum Kohlenstoffgerüst der CNTs, der Einfluss der mechanischen Verformung des CNTs als Reaktion auf die Anlagerung ist hingegen sehr gering. Die relevanten Bänder der Kobaltatome liegen leicht unterhalt der Fermi-Energie und sorgen bei der Integration in die Bandstruktur des CNTs für die Schließung der Bandlücke und somit für die Transformation eines vorher halbleitenden CNTs in ein leitendes. Diese Transformation konnte auch mit Simulationsrechnungen zum Elektronentransport bestätigt werden. Ferner wurden bei weiteren Rechnungen eine ausgeprägte Spinabhängigkeit der Bandstruktur ermittelt, welche noch weiterer Untersuchung bedarf.

Carbon nanotubes (CNTs) are a highly promising material for future interconnects. It is expected that the decoration of CNTs with Cu particles or also the filling of the interspaces between the CNTs with Cu instead of the currently used SiO2 can enhance the performance of CNT-based interconnects. Due to the high aspect ratio of CNTs an appropriate deposition technique has to be applied which is able to coat such structures uniformly. The current work is therefore considered with thermal atomic layer deposition (ALD) of CuxO from the liquid Cu (I) β-diketonate precursor [(nBu3P)2Cu(acac)] and wet oxygen at 135°C on variously pretreated multi-walled CNTs. The different in-situ pre-treatments of the CNTs with oxygen, water vapor and wet oxygen in a temperature range from 100 to 300°C at a pressure of 1.33 mbar have been carried out prior to the ALD to enable uniform nucleation on the otherwise chemical inert CNT surface. The reduction of the CuxO as well as the filling of the space between the CNTs is not part of this work. Variations of the oxidation temperature as well as the oxidation agents resulted in different growth modes of the CuxO. An oxidation with wet oxygen at 300°C yielded in a partially layer like growth of the CuxO. It is expected that this growth mode is connected to a partial destruction of the outer CNT shell due to the oxidation. However, the damage introduced to the CNTs was not high enough to be detected by Raman spectroscopy. For all other investigated pretreatments, the formation of nanoparticles (NPs) was observed by electron microscopy. This formation of CuxO NPs can be explained by the metal-tube-interaction. Furthermore, the NPs probably decorate defect sites of the CNTs due to their higher reactivity. Additionally, analysis of energy-dispersive X-ray spectroscopy and spectroscopic ellipsometry measurements suggests that the used precursor [(nBu3P)2Cu(acac)] requires reactive oxygen surface groups for initiating the ALD growth. The observation of layer-like growth of CuxO on CNTs pretreated with wet oxygen at 300°C appears promising for deposition processes of Cu seed layers on CNTs. However, more aggressive pretreatments at higher temperatures or with more aggressive oxidation agents could be required to enable layer like growth on the entire CNTs.

Next generation polymer composites that utilize the high electrical conductivity and tensile strength of carbon nanotubes are of interest. To effectively disperse carbon nanotubes into polymers, a more fundamental understanding of the polymer/nanotube interface is needed. This requires the development of new analytical methods and techniques for measuring the adhesion between a single molecule and the sidewalls of carbon nanotubes. Atomic Force Microscopy is an integral tool in the characterization of materials on the nanoscale. The objectives of this research were to: 1) characterize the binding force between single molecules and the backbone of a single walled carbon nanotube (SWNT), and 2) measure and interpret the mechanical response of carbon-based nano-objects to compressive loads using an atomic force microscope. To identify chemical moieties that bind strongly to the sidewall of the nanotubes, two experimental approaches have been explored. In the first, force volume images of SWNT paper were obtained using gold-coated AFM tips functionalized with terminally substituted alkanethiols and para-substituted arylthiols. Analysis of these images enabled quantification of the adhesive interactions between the functionalized tip and the SWNT surface. The resultant adhesive forces were shown to be dependent upon surface topography, tip shape, and the terminal group on the alkanethiol. The mechanical response of several single- and multi-walled carbon nanotubes under compressive load was examined with an AFM. When the scanner, onto which the substrate has been mounted, was extended and retracted in a cyclic fashion, cantilever deflection, oscillation amplitude and resonant frequency were simultaneously monitored. By time-correlating cantilever resonance spectra, deflection and scanner motion, precise control over the length of nanotube in contact with the substrate, analogous to fly-fishing was achieved. This multi-parameter force spectroscopy method is applicable for testing the mechanical and interfacial properties of a wide range of nanoscale objects. This research has led to a clearer understanding of the chemistry at the nanotube/polymer interface, as well as the mechanical response of nanoscale materials. A new force spectroscopic tool, multi-parameter force spectroscopy, should be extremely helpful in characterizing the mechanical response of a myriad of nanoscale objects and enable nanoscale devices to become a reality.

Optically transparent carbon based nanomaterials including graphene and carbon nanotubes(CNTs) are promising candidates as transparent conductive electrodes due to their high electrical conductivity coupled with high optical transparency, can be flexed several times with minimal deterioration in their electronic properties, and do not require costly high vacuum processing conditions. CNTs are easily solution processed through the use of surfactants sodium dodecyl sulfate(SDS) and sodium cholate(SC). Allowing CNTs to be deposited onto transparent substrates through vacuum filtration, ultrasonic spray coating, dip coating, spin coating, and inkjet printing. However, surfactants are electrically insulating, limit chemical doping, and increase optical absorption thereby decreasing overall performance of electrodes. Surfactants can be removed through nitric acid treatment and annealing in an inert environment (e.g. argon). In this thesis, the impact of surfactant removal on electrode performance was investigated. Nitric acid treatment has been shown to p-dope CNTs and remove the surfactant SDS. However, nitric acid p-doping is naturally dedoped with exposure to air, does not completely remove the surfactant SC, and has been shown to damage CNTs by creating defect sites. Annealing at temperatures up to 1000°C is advantageous in that it removes insulating surfactants. However, annealing may also remove surface functional groups that dope CNTs. Therefore, there are competing effects when annealing CNT electrodes. The impacts on electrode performance were investigated through the use of conductive-tip atomic force microscopy, sheet resistance, and transmittance measurements. In this thesis, the potential of graphene CNT composite electrodes as high performing transparent electrodes was investigated. As-made and annealed graphene oxide CNT composites electrodes were studied. Finally, a chemical vapor deposition grown graphene CNT composite electrode was also studied.

The present thesis entitled “Design and Synthesis of Novel Soft Composites from Physical Gels and Nanomaterials” deals with soft materials derived from low molecular weight gels and nanomaterials. Chapter 1 gives a general introduction and overview of the low molecular weight gel (LMOG) which forms the basis of the work. It delves with the history of research in physical gel field, design of different types of gelator molecules, their interesting self-assembly patterns, potential applications of these gelator molecules as well as challenges to design new gelator molecules. It also encompasses the relatively recent area of two component gel system to conveniently bypass the cumbersome synthetic protocol. The aspect of liquid crystallinity in the gel phase is also discussed to throw light on the pattern of assembly and potential uses of these materials. Towards the end there is a comprehensive discussion on the smart nanocomposites derived from LMOGs and nanomaterials. The design, synthesis and numerous applications of inorganic-organic hybrid composites are discussed. Chapter 2A describes the synthesis and characterization of a variety of fatty acid amides of different naturally occurring L-amino acids whose molecular structures are shown in Chart 2A.1. Some of them were found to form gels with various hydrocarbons. The gelation properties of these compounds were studied by a number of physical methods including FT-IR spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), differential scanning calorimetry, rheology and it was found that gelation was critically dependent on the fatty acid chain length and nature of the amino acid. Among them, L-alanine based gelators were found to be the most efficient and versatile as they self-assemble into a layered structure to form the gel network. Mechanisms for the assembly and formation of gels from these molecules are discussed. (Structural formula) Chart 2A.1. Molecular structures of various fatty acid amides of different amino acids. Chapter 2B describes efficient gelation of both aliphatic and aromatic hydrocarbon solvents by a fatty acid amide, n-lauroyl-L-alanine (Chapter 2B.1). In addition, this compound was found to gelate the binary solvent mixtures comprised of aromatic hydrocarbon e.g. toluene and aliphatic hydrocarbon e.g. n-heptane. SEM and AFM showed that the fiber thickness of the gel assembly increases progressively in the binary mixture of n-heptane and toluene with increasing percentage of toluene. The self- Chart 2B.1. Molecular structure of the gelator. assembly patterns of the gels in individual solvents, n-heptane and toluene are however, different. The toluene gel consists of predominantly one type of morphological species while n-heptane gel has more than one species leading to polymorphic nature of the gel. The n-heptane gel is thermally more stable than the toluene gel as evident from the measurement using differential scanning calorimetry. The thermal stability of the gels prepared in the binary mixture of n-heptane and toluene is dependent on the composition of solvent mixture. Rheology of the gels shows that they are shear-thinning material and show characteristic behavior of soft viscoelastic solids. For the gels prepared from binary solvent mixture of toluene and n-heptane, with incorporation of more toluene in the binary mixture, the gel becomes a more viscoelastic solid. The time sweep rheology experiment demonstrates that the gel made in n-heptane has faster gel formation kinetics than that prepared in toluene. Chapter 2C describes lyotropic mesophase formation by organogels of different fatty acid amides of L-alanine in aromatic solvents. The helical assembly, characteristic of the cholesteric mesophase was found to exhibit reflection bands in circular dichroism spectra. The reflection bands corresponded to the pitch of the helical arrangement of the gelator molecules in the aromatic solvent. Transmission Electron Microscopy (TEM) showed presence of twist in the gel fibres. Polarising optical microscopy of the organogel exhibited weak birefringence confirming lyotropic nature of the assembly. Chapter 3 deals with synthesis and characterization of a new class of molecules with molecular structures shown in Chart 3.1. Among a variety of amino acid based molecules only alanine and serine based molecules were found to form translucent gels in aliphatic hydrocarbons such as n-heptane. TEM showed presence of fiber like structures for alanine whereas serine based gelator produces unique network like structures. SEM of the dried gels exhibited presence of three dimensional fibrous networks to spongy globular cauliflower like structures depending on the molecular structure of the gelators. Rheological studies of the organogels showed that they behave like typical LMOG gels. The oscillatory rheological studies demonstrated that the L-serine based gelator, 5 formed more viscoelastic solid like gel than that of L-alanine based gelator, 1 in n-heptane. Chart 3.1. Molecular structures of different amino acid derivatives from 3,4,5-tri-dodecyloxybenzoic acid scaffold. Chapter 4A presents design and properties of new nanocomposites from LMOG and metal nanoparticles (Chart 4A.1). The profound influence of nanoparticle (NP) incorporation into physical gels was evident from various microscopic and bulk properties. The interaction of nanoparticles with the gelator assembly was found to depend critically on the capping agent coating the nanoparticles. TEM showed long range Chart 4A.1. Molecular structures of the gelator and various AuNPs synthesized. directional assembly of the certain AuNPs along the gel fibers. SEM of the dried gels and nanocomposites indicated that the morphological transformation in the composite microstructures depended profoundly on the capping agent of the nanoparticle. Differential Scanning Calorimetry showed that gel formation from sol postponed to lower temperature with incorporation of AuNPs having capping agents which were able to interact with the gel fibers. Rheological studies indicated that the gel-nanoparticle composites exhibit greater rigidity as compared to the naked gel only when the capping agents were able to interdigitate into the gelator assembly. Also, very low percentage of the AuNPs incorporation could switch the cholesteric mesophase of gel assembly, as evident from circular dichroism. We have been able to define a relationship between materials and molecular properties via manipulation of the molecular structures of NP capping agents. Chapter 4B discusses the design and preparation of novel organogel-carbon nanotube composites by incorporation of single-walled carbon nanotubes (SWNT) into physical gels formed by an L-alanine based Low Molecular Mass Organogelator (Chart 4B.1). The gelation process and the properties of the resulting nanocomposites were found to depend on the kind of SWNTs incorporated in the gels. With pristine SWNTs, only a limited amount could be dispersed in the organogels. Attempted incorporation of higher amounts of pristine SWNTs led to precipitation from the gel. To improve their solubility in the gel matrix, a variety of SWNTs functionalized with different aliphatic and aromatic chains were synthesized (Chart 4B.1). Scanning electron microscope images of the nanocomposites showed that the texture and organization of the gel aggregates were altered upon incorporation of SWNTs. The microstructures of nanocomposites were found to depend on the kind of SWNTs used. Incorporation of functionalized SWNTs into the organogels depressed the sol to gel transition temperature, with the n-hexadecyl chain functionalized SWNTs being more effective than the n-dodecyl chain functionalized counterpart. Rheological investigations of pristine SWNT containing gels indicated that the flow of nanocomposites became resistant to applied stress at a very low wt-% of SWNT incorporation. Again, more effective control of flow behavior was achieved with functionalized SWNTs possessing longer hydrocarbon chains. This happens presumably via effective interdigitation of the pendant chains with the fatty acid amides of L-alanine in the gel assembly. Also, the helical cholesteric mesophase formed by the toluene gel could be switched to a layer stacked assembly by doping functional SWNT. Remarkably, by using a near IR laser irradiation at 1064 nm for a short duration (1 min) at room temperature, it was possible to selectively induce a gel-to-sol phase transition of the nanocomposites, while prolonged irradiation (30 min) of the organogel under identical conditions did not cause gel melting. Chart 4B.1. Molecular structures of the gelator and different functionalized SWNT synthesized. Chapter 5A presents design of two component hydrogels and their potential utilization as a template for metal nanoparticle synthesis. Among a variety of acids and amines (Chart 5A.1) only stearic acid or eicosanoic acid when mixed with di- or oligomeric amines in specific molar ratios form stable gels in water. The formation of such hydrogels depends on the hydrophobicity of the fatty acid, and also on the type of amine used. The gelation properties of these two component systems were investigated using electron microscopy, FTIR, 1H NMR spectroscopy, differential scanning calorimetry (DSC) and both single crystal and cast film X-ray diffraction. FTIR spectral analysis suggests salt formation during gelation. 1H NMR of the gels indicates that the fatty acid chains are immobilized in the gel state and when the gel is melted, these chains regain their mobility. Analysis of DSC data indicates that increase in spacer length in the di-/oligomeric amine lowers the gel melting temperature. Two of these gelator salts developed into crystals and structural details of such systems could be secured by single-crystal X-ray diffraction analysis. The structural information of the salts thus obtained was compared with the XRD data of the self-supporting films of those gels. Such analyses provided pertinent structural insight on the supramolecular interactions that prevail within these gelator assemblies. From the crystal structure it is confirmed that the multilayered lamellar aggregates exist in the gel and it also showed that only one plane of symmetry is present in the gel state. Finally, the hydrogel was used as a medium for the synthesis of silver nanoparticles. The nanoparticles were found to position themselves on the fibers and produce a long ordered assembly of gel-nanoparticle composite (Figure 5A.1). Chart 5A.1. Structures and abbreviations of different acids and amines checked for gelation. Figure 5A.1. TEM images of gel-Ag-NP composite. (a) Ag-NP synthesized in hydrogel of SA-IBPA (1:3.5), (b) Magnified images of Ag-NP preferentially residing on gel fibers. Chapter 5B demonstrates the aptitude of supramolecular hydrogel formation using simple bile acids e.g. lithocholic acid (LCA) in aqueous solution containing di- or oligomeric amines (Chart 5B.1). By variation of the choice of the amines in such mixture the hydrogelation properties could be modulated. However, replacement of LCA by cholic acid or deoxycholic acid resulted in no hydrogelation. FT-IR studies show that the carboxylate and ammonium residues of the two components are primarily involved in salt formation. This promotes further assembly of the components reinforced by continuous Chart 5B.1. Structures and abbreviations of different bile acids and amines checked for gelation. hydrogen bonded network leading to gelation. Electron microscopy shows that the morphology of the gels of two component systems which also depends strongly on the amine part. Variation of amine component from the simple ethanediamine (EDA) to oligomeric amine with lithocholic acid changes the morphology of the assembly from long one dimensional nanotubes to three dimensional complex structures. Single crystal X-ray diffraction analysis with one of the amine-LCA complexes suggested the motif of fiber formation where the amines participate with the carboxylate and hydroxyl moiety through H-bonding and electrostatic forces. The rheological properties of this class of two component system provide clear evidence that this system is a shear-sensitive hydrogel and the flow behavior can be modulated varying the acid-amine ratio. From small angle neutron scattering study, it becomes clear that loose gel from LCA-EDA shows scattering oscillation due to the presence of non interacting nanotubules while for gels of LCA with oligomeric amine the individual fibers come together to form complex three dimensional structures of higher length scale.(For structural formula pl refer the pdf file)

Ab initio calculations of the electronic structure of freestanding Cu and Na nanowires with a diameter of few atoms are presented. The calculations are based on density functional theory in local density approximation using a Screened Korringa-Kohn-Rostoker-Green's function method. The method was extended for the description of quasi-onedimensional systems. Translational invariance in direction of the wire is assumed. The dependence of the bandstructure and the density of states from thickness and shape of the cross-section is discussed. The quantum confinement of the eigenstates is analysed. By comparing the results of the Na and Cu wires, the influence of the d-electrons is shown. Based on the Landauer theory of transport the conductance is obtained within a Green's function formalism. The numerical description of the conductance is tested for ideal translationally invariant Na and Cu wires. The influence of substitutional transition metal impurities on the electronic structure and the conductance of the 2x2 Cu wire is studied. A spin-dependent discussion is given for magnetic impurities. / Es werden ab initio Berechnungen der elektronischen Struktur freistehender Na- und Cu-Nanodrähte mit einem Durchmesser von wenigen Atomen präsentiert. Für die Berechnung wird eine Screened Korringa-Kohn-Rostoker-Grennsche Funktionsmethode genutzt, die auf der Spindichtefunktionaltheorie in lokaler-Spindichtenäherung basiert. Diese Methode wurde für die Beschreibung von quasieindimensionalen Systemen erweitert. Die Drähte werden als translationsinvariant in Drahtrichtung beschrieben. Es wird die Abhängigkeit der Bandstruktur und der Zustandsdichte von der Dicke und der Form des Querschnitts diskutiert. Das Quantenconfinement der Eigenzustände wird analysiert. Durch den Vergleich der Resultate für den Na- und den Cu-Draht kann der Einfluss der d-Elektronen gezeigt werden. Ausgehend von der Landauer-Theorie des Transports wird der Leitwert im Rahmen eines Greenschen Funktions-Formalismus berechnet. Diese neue numerische Beschreibung des Leitwertes wird an idealen translationsinvarianten Drähten getestet. Es wird der Einfluss von substitutionellen 3d-Übergangsmetall-Störungen auf die elektronische Struktur und auf den Leitwert von 2x2-Cu-Drähten studiert. Im Fall magnetischer Defekte wird dieser Einfluss spinabhängig diskutiert.

Deux thématiques sont développées dans la présente thèse. Tout d'abord, des surfaces de molybdène nues et carburées sont étudiées à l'aide de calculs basés sur la théorie de la fonctionnelle de la densité – DFT – appliquée aux systèmes périodiques. Les propriétés électroniques et structurales des surfaces 100, 110 et 111 du molybdène cristallin et p(1x1)-C, c(2x2)-C et c(3√2x√2)R45°-C Mo(100), p(4x4)-C Mo(110) et p(6x1)-C Mo(111) sont déterminées. L'activité de la surface p(4x4)-C Mo(110) vis-à-vis de l'adsorption de CO est abordée par la détermination des modes de vibration du monoxyde de carbone coordiné à divers sites de surface. Le modèle de surface proposé est validé par une comparaison des données expérimentales et théoriques.<br /> L'étude de la fonctionnalisation de surfaces carbonées - graphite et nanotube (8,0) - par un atome de métal de transition est réalisée par des calculs DFT. Il est déterminé que les atomes de Cr, Mn et Cu sont physisorbés alors que les autres atomes de la série 3d sont chimisorbés. L'occupation de l'orbitale 4s pour Cr, Mn et Cu conduit à une répulsion métal-surface, quelque soit la courbure du plan graphitique. Les surfaces d'énergie potentielle sont déterminées pour évaluer les barrières de diffusion. Sc, Ti, Fe et Co sont les métaux susceptibles d'être isolés en surface. Les autres diffusent (formation d'aggrégats). Le magnétisme, l'énergie d'adsorbtion et la structure géométrique sont analysés à l'aide de l'étude des densités d'états, des charges de Bader et de diagrammes orbitalaires de molécules organométalliques modèles. <br /> Finalement, l'activation du dihydrogène par un métal 3d de surface est étudiée. Des complexes dihydrures et d'hydrogène moléculaire sont localisés en surface. La faible élongation de la liaison s HH est observée préférentiellement pour Fe, Co et Ni tandis que la rupture de la liaison apparaît pour Sc, Ti et V. La saturation de certains métaux par adsorption de plusieurs molécules d'hydrogène est entreprise. Il est montré que ces matériaux hypothétiques pourraient stocker l'hydrogène.<br /> La création d'un cluster d'ordinateurs pour le calcul numérique est présentée. L'originalité consiste à utiliser des ordinateurs dédiés à l'enseignement et utilisables en dehors de ces périodes.

Le spectre d'absorption optique des nanotubes de carbone semiconducteurs est analysé par une approche mathématique rigoureuse. Un modèle quantique décrivant le nanotube est suggéré et est étudié à l'aide de la théorie de perturbation. En utilisant la petitesse du rayon du tube, le problème est d'abord réduit à une dimension. La théorie de la réponse linéaire permet ensuite d'exprimer le spectre d'absorption en fonction des états propres de l'Hamiltonien unidimensionel associé au tube. <br />Plusieurs arguments physiques ainsi que l'utilisation intensive de la théorie de perturbation amènent l'étude de l'Hamiltonien unidimensionel, à grand nombre de particules, à être réduite à celle de l'Hamiltonien de l'exciton, système composé de deux particules de charges opposées. Des expressions quasi-analytiques pour les états propres de ce système, dépendantes du rayon du tube, sont obtenues perturbativement. Les pics d'absorption de lumière correspondant à des énergies dans la lacune entre bande de valence et bande de conduction du nanotube semiconducteur sont alors reliés à la présence d'excitons et la localisation des pics est donnée en fonction du rayon du tube par une expression approchée avec un terme d'erreur contrôlé.