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Au cours de cette thèse, la physique des systèmes en interaction à été étudié expérimentalement à partir de gaz froids d'atomes de Rydberg. Les atomes de Rydberg sont des atomes dans un état fortement excités et ils ont la propriété d'interagir fortement du fait d'interactions électrostatiques à longue portée. Le premier résultat majeur de cette thèse est l'observation expérimentale d'un processus à quatre corps. Ce processus consiste en l'échange d'énergie interne entre quatre atomes de Rydberg induit par leurs interactions mutuelles. Il a été possible, en plus de son observation expérimentale, de décrire théoriquement ce processus, au niveau quantique. L'excitation par laser des gaz d'atomes de Rydberg en forte interaction a aussi été étudiée durant cette thèse. Cette situation donne lieu à de très intéressants comportements à N-corps. Ce sujet d'intérêt fondamental pourrait aussi amener à d'éventuelles applications pour la réalisation de simulateurs quantiques ou de sources de lumière non classiques. Un second résultat majeur de cette thèse est l'observation expérimentale d'une statistique fortement sub-poissonienne, i.e corrélée de l'excitation Rydberg. Ce résultat confirme le caractère à N-corps de tels systèmes. Le troisième résultat majeur de cette thèse est le développement d'un modèle théorique pour l'excitation par laser des gaz d'atomes de Rydberg en forte interaction. En utilisant les états quantiques dit états collectifs de Dicke, il a été possible de mettre au jour de nouveaux mécanismes liés au comportement à N-corps de ces sytèmes atomiques en forte interaction. / Uring this thesis, the Physics of interacting systems has been investigated experimentally using Cold Rydberg gases. Rydberg atoms are highly excited atoms and have the property to interact together through long-range electrostatic interactions.The first highlight of this thesis is the direct experimental observation of a 4-body process. This process consists in the exchange of internal energy between 4 Rydbergs atoms due to their mutual interactions. In addition to its observation, it has been possible to describ this process theoretically at a quantum level.The laser excitation of strongly interacting Rydberg gases has been also investigated during this thesis. In this regime, the interactions between Rydberg atoms give rise to very interesting many-body behaviors. In addition to fundamental interest, such systems could be used to realyze quantum simulators or non-classical light sources.A second highlight of this thesis is the experimental observation of a highly sub-poissonian, i.e correlated, excitation statistics. This result confirms the many-body character of the investigated system.The third highlight of this thesis is the development of a theoretical model to describ the laser excitation of strongly interacting Rydberg gases. Using the so-called Dicke collective states it has been possible to point out new mechanismes related to the many-body character of strongly atomic interacting systems.

<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>

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.