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The adiabatic or Born-Oppenheimer approximation is often used in molecular calculations to simplify the solution to the Schrodinger equation. The basis of the approximation is the large difference in the relative motions of the nuclei and electrons in the molecule-the electrons are able to respond almost instantly to the movements of the nuclei. Thus, the nuclei may be regarded as being fixed in a certain position and the Schrodinger equation can then be solved using the potential obtained by solving the electronic problem at fixed nuclear configuration. A similar argument can be used to decouple the angular and radial motions of many van der Waals complexes because, like nuclei in molecules, the radial motions in many van der Waals complexes are strongly localized. Fixing the radial separation between the atoms and molecules in the complex to a particular value results in a Schrodinger equation that is much simpler to solve because it is only dependent on angles. van der Waals complexes containing helium atoms, however, present a dilemma because the extremely weak interactions present also lead to large amplitude radial as well as angular motions. Because the basis of the adiabatic approximation is a large difference in time scale between the angular and radial motions, the validity of the adiabatic approximation for helium complexes is uncertain. In this thesis, the adiabatic separation of angular and radial motion is shown to be accurate for extremely floppy complexes of helium by demonstrating its use on the van der Waals molecule He-HCN. A major application of this method is expected to be the quick calculation of approximate wave functions for Diffusion Monte Carlo studies of the rotation of impurity molecules inside ultra-cold droplets of helium. The method presented here is significantly faster than other methods (e.g., Variational Monte Carlo) that have been used to calculate approximate wave functions for Diffusion Monte Carlo.

London or dispersion interactions are weak van der Waals (vdW) interactions. They are important in determining the structure and properties of many chemical and biochemical systems. In this thesis, an optimizer using the nonempirical generalized gradient approximation (GGA) functional PW86+PBE+XDM, to capture van der Waals interactions, is presented. The work in this thesis covers the assessment of a variety of basis sets for their ability to reproduce accurate GGA repulsive and binding energies. Selected basis sets were then used to compute binding energies of 65 vdW complexes at equilibrium. This functional was also tested for binding energies of two sets of vdW complexes at distorted geometries. The last part deals with forces to investigate their accuracy using PW86+PBE+XDM in order to build an optimizer for vdW complexes using a nonempirical DFT method. Eventually, after confirming a high reproducibility of the optimizer on the geometries and binding energies, it was used in two biologically relevant applications. This optimizer is a unique tool to compute deformation energies with a nonempirical DFT method. The second part of this thesis covers a biologically relevant application where a conventional DFT is used. This application is related to the carrier of the genetic codes in living cells, DNA. DNA undergoes harmful mutations under external perturbations such as applied external electric fields. In this study, DNA base pairs were first mimicked by a simpler model, namely, the formic acid dimer. The effect of applied external electric fields on the geometries of the formic acid dimer is studied. The effect of these applied fields on the potential energy surface, the barrier height and the frequency of the double proton transfer in the formic acid dimer are also investigated. The study was then repeated on DNA base pairs to study the effect of an external applied electric field on the tunneling corrected rate constants of the double proton transfer reactions in AT and GC.

The question posed in this work is how one would model and predict the rotational spectrum of open-shell open-shell van der Waals complexes. There are two secondary questions that arise: the nature of radical-radical interactions in such systems and the modelling of the large amplitude motion of the constituent molecules. Four different systems were studied in this work, each providing part of the answer to the main question. Starting with the large amplitude motion, there are two theoretical approaches that may be adopted: to either model the whole complex as a semi-rigid molecule, or to perform quantum dynamical calculations. We recorded and analysed the rotational spectrum (using Fourier transform microwave spectroscopy) of the molecule of tertiary butyl acetate (TBAc) which exhibits a high degree of internal rotation; and of the weakly-bound complex between a neon atom and a nitrogen dioxide molecule (Ne-NO2). We used the semi-rigid approach for TBAc and the quantum dynamical approach for Ne-NO2. We also explored the compatibility of these two approaches. Moreover, we were able to predict and analyse the fine and hyperfine structure of the Ne-NO2 spectrum using spherical tensor operator algebra and the results of our dynamics calculations. To explore the nature of the interactions in an radical-radical van der Waals complex we calculated the PESs of the possible states that the complex may be formed in, when an oxygen and a nitrogen monoxide molecule meet on a plane using a number of high level ab initio methods. Finally, our conclusions were tested and applied when we performed the angular quantum dynamics to predict the rotational spectrum of the complex between an oxygen and a nitrogen dioxide molecule, and account for the effect of nuclear spin statistics in that system.

Les complexes de van der Waals sont des entités constituées de différentes molécules liées par des interactions faibles (~kJ/mol). Ces agrégats présentent une réactivité particulière et jouent un rôle essentiel dans les phénomènes de solvatation et nucléation. Des moyens expérimentaux et théoriques pour étudier les complexes de van der Waals et en particulier ceux contenant de l’acétylène ont donc été développés dans ce travail. Nous avons utilisé et amélioré un montage expérimental appelé FANTASIO+ (Fourier trANsform, Tunable diode and quadrupole mAss spectrometers interfaced to a Supersonic expansIOn). Ce montage, composé d’un jet supersonique et d’un spectromètre à temps de déclin permet la production et la détection de ce genre de complexes. Le jet supersonique consiste en une détente adiabatique d’un gaz et assure par refroidissement à quelques Kelvins la production de complexes. La spectrométrie à temps de déclin mesure l’absorption d’un laser infra-rouge par ces molécules cibles assurant ainsi leur détection. <p>Une diode laser nous a permis d’exciter deux fois l’étirement CH de l’acétylène. Nous avons pu détecter et analyser le spectre de vibration-rotation des complexes suivants :C2H2-Ne, C2H2-Ar, C2H2-Kr, C2H2-CO2, C2H2-N2O, et C2H2-C2H2. La molécule C2H2-CO2 et des isotopologues de C2H2-C2H2 ont également été étudiés à plus basse énergie durant un séjour à Calgary au Canada. Nos études ont démontré que ces complexes restaient liés à une énergie pouvant aller jusqu’à 130 fois l’énergie d’interaction entre les deux monomères. L’obtention de données à haute résolution spectrale permet également d’obtenir des données de références pour la validation de modèles théoriques et la planétologie. En particulier, la première détection de C2H2-Kr permettra peut-être une future observation de cet agrégat dans des atmosphères planétaires comme par exemple Titan. <p>Pour avoir une approche globale de ces systèmes nous nous sommes tournés vers les outils de la chimie quantique pour caractériser l’interaction entre les entités du complexe. Des tests méthodologiques approfondis nous ont permis d’évaluer avec exactitude les surfaces d’énergie potentielle intermoléculaire des complexes contenant une molécule d’acétylène et un atome de krypton ou de xénon. <p><p>van der Waals complexes are molecular systems in which the units or molecules are held together by weak interactions (~kJ/mol). These complexes present a peculiar reactivity and play a critical role in solvation and nucleation. Theoretical and experimental means were developed in this work to study such systems and in particular, complexes containing acetylene. In the context of this work the FANTASIO+ (Fourier trANsform, Tunable diode and quadrupole mAss spectrometers interfaced to a Supersonic expansIOn) experimental set-up was used and improved. This set-up, composed of a supersonic expansion and a cavity ring-down spectrometer, provides a way to produce and detect these complexes. The supersonic expansion is an adiabatic expansion which produces the complexes by cooling of the gas to few Kelvin. The CRDS set-up detect those complexes by infra-red laser absorption.<p>Using laser diode to doubly excite the CH stretch of acetylene, one then succeeded to observe and analyze the ro-vibrational spectra of the following complexes: C2H2-Ne, C2H2-Ar, C2H2-Kr, C2H2-CO2, C2H2-N2O, et C2H2-C2H2. The C2H2-CO2 and isotopologues of C2H2-C2H2 were also studied at lower energy during a three months stay in Calgary, Canada. Our studies demonstrated that complexes stayed bound even at an energy 130 times higher than the energy holding the entities together. The high resolution data obtained during this work is also useful to validate theoretical models and planetology. The first detection of the C2H2-Kr complex, in particular, could allow its future detection in other atmospheres, i.e. on Titan.<p>To have a global approach to these systems, the quantum chemistry tools were used to characterize the interaction between the partners of the complexes. Numerous methodological tests allowed us to accurately evaluate the intermolecular potential energy surfaces of the complexes containing an acetylene molecule and a krypton or a xenon atom. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

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