Rozprawy doktorskie na temat „Oppenheimer Molecular”

The research over-viewed in this dissertation concerns very accurate variational calculations of the molecular systems with more than two electrons under the assumption of the Born-Oppenheimer (BO) approximation. The centerpiece of this research is the use of explicitly correlated Gaussian (ECG) basis functions with floating centers to generate the potential energy curve (PEC) and potential energy surface (PES) of the considered molecular systems. One challenge of such calculations is the occurrence of the linear dependency between basis functions in the process of basis set optimization. The BO PECs generated with ECG basis sets were limited to two-electron molecular systems for a few decades prior to the implementation of the author's approaches to this issue. These approaches include methods for a partial remedy to linear dependence, better guessing of initial basis functions, permanently removing the restriction of memory usage in parallel computer systems, and efficiently paralleling the calculations. The approach effectively utilizing the super computer systems yields benefits not only to the ECG calculations but could also be useful in the fields that require the significant amount of the computational resources. These procedures were implemented in computer codes that were run quite extensively on several parallel computer systems during the period of the author's Ph.D study. The calculated adiabatic PECs and the rovibrational energy levels are proven to be the most accurate ones to date. The dissertation is primarily based on the content of the papers that were published in co-authorship with my scientific advisor and other collaborators in several scientific journals. It also includes some details that were not considered in the publications but are essential for the completeness and good understanding of the presented work. In order to provide readers an insight into the development of the ECG based BO molecular calculation, the published results of many calculations are classified and presented in a comprehensive way.

In our previous work S. Bubin et al., Chem. Phys. Lett. 647, 122 (2016), it was established that complex explicitly correlated one-center all-particle Gaussian functions (CECGs) provide effective basis functions for very accurate nonrelativistic molecular non-Born-Oppenheimer calculations. In this work, we advance the molecular CECGs approach further by deriving and implementing algorithms for calculating the leading relativistic corrections within this approach. The algorithms are tested in the calculations of the corrections for all 23 bound pure vibrational states of the HD+ ion.

A constante emissão de CO2 na atmosfera devido a fontes antropogênica despertou uma preocupação crescente em função da sua atuação no efeito estufa. Um número crescente de metodologias para redução da concentração deste gás na atmosfera vem sendo proposta e uma alternativa atrativa é a da inserção do CO2 em anéis epóxidos para formação de carbonatos cíclicos. Apesar de já existirem inúmeros trabalhos a respeito destas reações, o mecanismo pelo qual elas ocorrem não está completamente esclarecido. Neste trabalho é apresentado o estudo mecanístico da cicloadição de CO2 em diferentes epóxidos catalisada por líquidos iônicos haletos de alquil-imidazólios, CnMIm X (n = 1, 2, 3, 4 e X = Cl, Br, I), através da Teoria do Funcional da Densidade empregando-se o funcional !B97X-D e o conjunto de base 6-31G(d,p) e LanL2DZ (somente para o I). Propuseram-se duas rotas distintas para o mecanismo, uma composta por três etapas e outra composta por somente duas etapas. Ambas as rotas tiveram a primeira etapa como sendo a mais energética e correspondendo à abertura do anel epóxido e mostraram ser competitivas entre si energeticamente. Esta etapa mostrou depender de ambos cátion e ânion do catalisador para ocorrer, onde uma ligação de hidrogênio não clássica com o H2 do imidazólio aparece no estado de transição. Verificou-se que no geral a energia de ativação da reação diminui com o aumento da cadeia alquílica do cátion imidazólio assim como diminui com o aumento do caráter nucleofílico do haleto (Cl > Br > I). O substituinte do anel epóxido também exerce influência sobre a energia de ativação da reação, porém não há uma tendência bem definida. Constatou-se que o sítio mais favorável para ataque nucleofílico é o carbono não substituído do anel epóxido tanto pela diferença de energia quanto por análise de índices de reatividade de Fukui e de interações não covalentes. Uma análise de 14 funcionais da densidade e do método perturbativo de segunda ordem MP2 em comparação ao método composto G4MP2 revelaram a forte dependência das energias de ativação com o método empregado. Através de cálculos de dinâmica molecular clássica foi possível estudar dinamicamente o sistema brometo de 1-butil-3-metil imidazólio, o óxido de estireno e o CO2 e notou-se a formação de duas fases com a presença de uma interface. Adicionalmente, observou-se que a probabilidade da reação ocorrer no bulk do líquido iônico é maior, pois a proporção catalisador/substrato é maior nesta região. Por meio da dinâmica molecular de Born-Oppenheimer constatou-se que o anel epóxido também pode ser ativado através de interações com os hidrogênios H4 e H5 do anel imidazólio.
The constant emission of CO2 into the atmosphere due to anthropogenic sources has generated a growing concern regarding the greenhouse effect. Many methodologies to reduce the atmospheric CO2 concentration have been proposed and an alternative is the insertion of CO2 into epoxides to form cyclic carbonates. Although there are a lot of studies in this area, the reaction mechanism by which they occur is still unclear. In this work the cycloaddition mechanism of CO2 into different epoxides catalyzed by alkyl-imidazolium halide ionic liquids, CnMIm X (n = 1, 2, 3, 4 e X = Cl, Br, I), is presented. Density Functional Theory in conjunction with the functional !B97X-D and 6-31G(d,p) and LanL2DZ (for I atoms) basis sets were employed. Two distinct routes were proposed for the mechanism: one composed of three steps and another composed by only two steps. Both routes showed that the first step regarding the epoxide ring opening is the determined one and they are energetically competitive with each other. This step depends on both cation and anion from the catalyst to proceed through a non-classical hydrogen bond in the transition state. It was found that the activation energy decreases with the chain length of the alkyl group from the imidazolium ring as well as with the nucleophilic character of the halide (Cl > Br > I). The epoxide ring substituent also exerts influence on the activation energy of this reaction, but there is no well defined behaviour. The most favourable site for nucleophilic attack is the non-substituted epoxide ring carbon as was shown by the reaction energy difference and through reactive Fukui index and non-covalent interaction (NCI) analysis. 14 exchange-correlation density functionals were investigated and compared to the well established second order perturbation theory (MP2) method and G4MP2 composite method. One found out that the activation energies strongly depends on the chosen method. Through classical molecular dynamics it was possible to study the system 1-butyl-3-methyl-imidazolium bromide together with styrene oxide and CO2 e the formation of two phases with the presence of an interface was observed. Additionally, it was shown that the probability of the reaction to occur in the ionic liquid bulk is bigger because the catalyst/substrate proportion is bigger in this region. Born-Oppenheimer molecular dynamics was used to prove that the H4 and H5 hydrogen atoms from the imidazolium ring may interact with the oxygen atom from the epoxide and activate the C–O bond for the reaction to proceed.

Dans cette thèse, l'étude de la dépostion des molécules de ferrocène sur un substrat de Cu(111) par des simulations de dynamique moléculaire par premiers principes, en particulier, la dynamique moléculaire utilisant l'approche de Born-Oppenheimer (BOMD: Born-Oppenheimer Molecular Dynamics) et celle utilisant la fonctionnelle de l'énergie libre (FEMD: Free Energy Molecular Dynamics), combinées avec les études expérimentales par microscopie à effet tunnel (STM) à basse température et à courant constant ont montré que ces molécules de ferrocène peuvent être physisorbées sur un substrat de cuivre sans donner lieu à une dissociation moléculaire. Ce qui constitue un système idéal pour étudier la dynamique des états d'interfaces et leur réactivité par rapport à la déposition d’atomes métalliques. En particulier, la déposition d'un atome de Cuivre au dessus d'une molécule de ferrocène équilibrée sur le substrat de cuivre, conduit à un transfert de charges de cet atomes vers le substrat de Cu(111). On montre aussi que ces états d'interfaces ont le comportement bidimensionnel d'un gas d'électrons libres
First-principles simulations studies, in particular Born-Oppenheimer molecular dynamics (BOMD) and free energy molecular dynamics (FEMD), combined with low-temperature scanning tunneling microscopy (STM) and spectroscopy reveal a non dissociative physisorption of ferrocene molecules on a Cu(111) surface, giving rise to ordered molecular layers. At the interface, a 2D-like electronic band is found, which shows an identical dispersion as the Cu(111) Shockley surface-state band. Subsequent deposition of Cu atoms forms charged organometallic compounds that localize interface-state electrons

Ce travail, effectué dans le cadre d’une collaboration entre l’IPN d’Orsay et EDF, contribue aux études destinées à améliorer la compréhension du comportement des radioéléments en production (centrale en fonctionnement) et à l’aval du cycle électronucléaire (stockage géologique profond des déchets). Le comportement et l’évolution des radioéléments sont fortement dépendants des interactions aux interfaces eau / surface minérale, phénomènes complexes et souvent difficiles à caractériser in situ (en particulier, dans le cas du circuit primaire des centrales REP). La dynamique moléculaire basée sur la théorie de la fonctionnelle de la densité apporte des éléments de compréhension sur l’évolution des structures d’équilibre en prenant en compte explicitement la solvatation et les effets de la température sur les mécanismes d’interaction. Dans un premier temps, le comportement de l’ion uranyle en solution et à l’interface d’un système modèle eau / TiO2 à température ambiante a été simulé et validé par la confrontation avec des résultats expérimentaux et des calculs de DFT statiques. Dans un deuxième temps, cette approche a été employée sur ce même système, à des fins prédictives, pour étudier l’effet d’une élévation de la température. La rétention de l’ion augmente avec la température en accord avec les données expérimentales obtenues sur d’autres systèmes, et conduit également à une modification du complexe de surface. Dans un troisième temps, une étude similaire a été effectuée à l’interface eau / NiO, produit de corrosion présent dans le circuit primaire des centrales nucléaires, pour lequel peu de données expérimentales sont disponible actuellement
This study, performed within the framework of an EDF and IPN of Orsay partnership, contributes to the studies intended to improve the understanding of the radioelement behaviour in service (nuclear power plant) and at the end of the uranium fuel cycle (deep geologic repository). The behaviour and the evolution of radioelement depend mainly on the interactions at the water / mineral interfaces, which are complex and often difficult to characterize in situ (in particular, in the PWR primary circuit). Molecular dynamic simulations based on the Density Functional Theory provide some insight to understand the evolution of the structures against the solvation and the effects of the temperature on the interaction mechanisms. At first, the behaviour of the uranyl ion at room temperature in solution and at the water / TiO2 interface, as a system model, has been studied and validated by the systematic comparisons with the experimental and static DFT calculations data. Secondly, this approach was used on the same system, in predictive purposes, to study the effect of a temperature rise. The retention of the ion increases with the temperature in agreement with the experimental data obtained on other systems, and led also to a modification of the surface complex. Finally, a similar study has been performed at the water / NiO interface, which corresponds to a corrosion product present in the primary circuit of nuclear power plants, but for which few experimental data are currently available

The accuracy of a quantum chemical calculation inherently depends on the ability to account for the completeness of the one- and n-particle spaces. The size of the basis set used can be systematically increased until it reaches the complete one-particle basis set limit (CBS) while the n-particle space approaches its exact full configuration interaction (FCI) limit by following a hierarchy of electron correlation methods developed over the last seventy years. If extremely high accuracy is desired, properly correcting for very small effects such as those resulting the Born-Oppenheimer approximation and the neglect of relativistic effects becomes indispensable. For a series of chemically interesting and challenging systems, we identify the limits of conventional approaches and use state-of-the-art quantum chemical methods along with large basis sets to get the “right answer for the right reasons.” First, we quantify the importance of small effects that are ignored in conventional quantum chemical calculations and manage to achieve spectroscopic accuracy (agreement of 1 cm−1 or less with experimental harmonic vibrational frequencies) for BH, CH+ and NH. We then definitively resolve the global minimum structure for Li₆ , Li₆⁺ , and Li₆- using high accuracy calculations of the binding energies, ionization potentials, electron affinities and vertical excitation spectra for the competing isomers. The same rigorous approach is used to study a series of hydrogen transfer reactions and validate the necessary parameters for the hydrogen abstraction and donation steps in the mechanosynthesis of diamondoids. Finally, in an effort to overcome the steep computational scaling of most high-level methods, a new hybrid methodology which scales as O(N⁵) but performs comparably to O(N⁶) methods is benchmarked for its performance in the equilibrium and dissociation regimes.

The procedures and results of experimental and/or theoretical studies of four transient molecules, GeO, WO, BeH, and MgH are reported in the thesis. Two of them, GeO and WO, are diatomic molecules composed of relatively heavy atoms, and the other two are diatomic molecules with hydrogen as one of their component atoms. The GeO species was generated using a high temperature furnace. The rovibrational spectrum of five isotopomers were detected in emission using a Bruker IFS 120 HR Fourier transform spectrometer. Combined-isotopomer Dunham-type molecular constants have been derived for GeO using the DSParFit computer program. Analysis shows that the Born-Oppenheimer approximation is valid, as expected, for a molecule containing heavy atoms. The WO molecule was generated using a microwave discharge cell, and the spectra of electronic transitions of various systems were detected in emission using both the Bruker IFS 120 HR Fourier transform spectrometer at Waterloo and the McMath Pierce One-Meter Fourier transform spectrometer at the National Solar Observatory in Arizona. The ground electronic state has been confirmed to be X³Σ^- based on the analysis of seven 0-0 bands. BeH and MgH are typical molecules with hydrogen as one of their component atoms, and the effects of Born-Oppenheimer breakdown were expected. Both of these molecules have rotational perturbations in their excited electronic states. A 'new' method of data processing was used, i. e. , treating the electronic data as if they were from fluorescence series. Thus the harmful influence of the perturbed upper electronic states on the ground electronic state molecular constants is eliminated. By using the DSParFit computer program, accurate sets of combined-isotopomer Dunham-type molecular constants have been derived for the ground electronic states of the two molecules, and Born-Oppenheimer breakdown correction terms have been obtained.

General formalism for the application of explicitly correlated Gaussian-type basis functions for nonadiabatic calculations on many-body systems is presented. In this approach the motions of all particles (electrons and nuclei) are correlated at the same time. The energy associated with the external degrees of freedom, i.e., the motion of the center-of-mass, is eliminated in an effective way from the total energy of the system. Methodology for construction of the many-body nonadiabatic wave function and algorithms for evaluation of the multicenter and multiparticle integrals involving explicity correlated Gaussian cluster functions are derived and computationally implemented. Then analytical derivation of multi-center and multi-particle integrals for explicitly correlated Cartesian Gaussian-type cluster functions is demonstrated. The evaluation method is based on application of raising operators which transform spherical cluster Gaussian functions into Cartesian Gaussian functions. Next, the Newton-Raphson procedure for optimization of the non-linear parameters (Gaussian exponents) appearing in the Gaussian-type cluster functions is developed. The procedure employs the first and second analytical derivatives of the variational functional with respect to the Gaussian exponents. The computational implementation of Newton-Raphson optimization procedure is described and some numerical calculations are presented. Finally, the methodology for generating higher nonadiabatic rotational states is presented.

Ce travail est destiné au développement de méthodes approchées de chimie quantique capables de traiter des systèmes biologiques de grande taille. En particulier, nous réalisons des simulations de dynamique moléculaire dans l'approximation de Born-Oppenheimer, permettant une description quantique de l'Hamiltonien électronique du système dans son entier : SEBOMD (SemiEmpirical Born-Oppenheimer Molecular Dynamics). Notre approche se base sur un Hamiltonien électronique semiempirique (SE). L'une des principales difficultés rencontrées lors d'une simulation SEBOMD de la phase condensée est représentée par le choix de la méthode SE. La plupart des méthodes courantes ne permettant pas une bonne description de certaines interactions fondamentales, nous avons développé une nouvelle approche. Cette méthode, dénommée PM3-PIF3, a été appliquée à l'étude par dynamique moléculaire de molécules organiques dans l'eau. Les résultats obtenus montrent que notre méthode est appropriée pour le traitement de molécules comportant des groupements hydrophobes et/ou hydrophiles en milieu aqueux. L'analyse des propriétés électroniques et vibrationnelles de ces molécules en présence du solvant valide également nos résultats vis-À-Vis d'autres études expérimentales et théoriques présentes dans la littérature. Finalement, nous nous sommes intéressés au processus d'autoprotolyse de l'eau en milieux confinés. Après avoir discuté du choix de l'Hamiltonien SE à utiliser pour cette étude, nous avons caractérisé le transfert de proton dans un agrégat d'eau. Nous avons établi une corrélation entre l'énergie libre associée à la première étape de ce transfert et certaines propriétés physiques collectives
The present work is devoted to the development of approximate quantum chemistry methods that are suitable to treat biological systems of large size. In particular, we run molecular dynamics under the Born-Oppenheimer approximation, allowing a quantum mechanical description of the electronic Hamiltonian of the full system: SEBOMD (SemiEmpirical Born-Oppenheimer Molecular Dynamics). Our method is based on a semiempirical (SE) electronic Hamiltonian. One of the key issues arising in a condensed phase SEBOMD simulation is represented by the choice of the SE method. Since most of the currently available approaches fail in describing some relevant intermolecular interactions, we developed a new correction of SE Hamiltonians. This method, which we named PM3-PIF3, was applied to study the molecular dynamics of organic molecules in water. The results that we obtained showed that our technique is suitable to treat molecules having hydrophobic and/or hydrophilic groups in an aqueous medium. The analysis of the electronic and vibrational properties of these molecules in the presence of the solvent validates our results with respect to experimental and theoretical studies in the literature. Finally, we investigated the water self-Dissociation process in confined environments. After discussing the choice of the SE Hamiltonian to be used for this purpose, we characterized the proton transfer in a water cluster. We established a correlation between the free energy of the first step of this process and some collective physical properties

Semiclassical and Born-Oppenheimer approximations are used to provide uniform error bounds for the energies of diatomic molecules for bounded vibrational quantum number n and large angular momentum quantum number l. Specifically, results are given when (l + 1) < κ𝛜⁻³/². Explicit formulas for the approximate energies are also given. Numerical comparisons for the H+₂ and HD+ molecules are presented.
Ph. D.

We discuss the physical problem of a molecule interacting with an electromagnetic field pulse and model the problem using a time-dependent perturbation of the Born-Oppenheimer approximation to the Schrodinger equation. Using previous results that develop asymptotic series solutions in the Born-Oppenheimer parameter ε, we derive a formal Dyson series expansion in the perturbation parameter μ, which is proportional to the electromagnetic field strength. We then prove that this series is asymptotically accurate in both parameters, provided that the Hamiltonian for the electrons has purely discrete spectrum. Under more general hypotheses, we show that the series is accurate to first order in μ, and that it is accurate to one higher order if we place conditions on the abruptness of the EM pulse. We also show how this series development provides a justification for the Franck-Condon factors in the case of a diatomic molecule.
Ph. D.

Au moyen de l'approximation de born-oppenheimer, on etudie la diffusion d'une molecule diatomique a partir de certains canaux a deux amas. En projetant l'hamiltonien p de cette molecule sur plusieurs etats electroniques d'une decomposition en deux amas, on construit un operateur p#a#d, dit adiabatique. Grace a cet operateur p#a#d on obtient, par la methode de mourre, dans une certaine bande d'energie, un theoreme d'absorption limite particulier pour l'operateur p. En considerant la somme des rapports de la masse des electrons a celles des noyaux comme un petit parametre, on approxime, dans certaines conditions, la valeur au bord de la resolvante de l'hamiltonien p par celle de l'operateur p#a#d. Le point nouveau pour ce resultat est que l'operateur p#a#d considere fait intervenir plusieurs niveaux electroniques. La methode utilisee permet egalement d'obtenir un theoreme d'absorption limite semi-classique pour un operateur matriciel de schrodinger et l'operateur de dirac avec champ electrique scalaire. Grace a cette approximation de la resolvante de l'operateur p, on generalise une approximation semi-classique d'operateurs d'onde adiabatiques. L'etude semi-classique de cette resolvante permet surtout d'etudier des sections efficaces totales, a angle d'incidence fixe, et d'en approximer certaines par des sections adiabatiques correspondantes. En particulier, ceci est realise pour certains canaux d'entree et de sortie differents du fait que plusieurs niveaux electroniques soient pris en compte

We study the Born-Oppenheimer approximation for a symmetric linear triatomic molecule in two space dimensions. We compute energy levels up to errors of order ε⁵, uniformly for three bounded vibrational quantum numbers n₁, n₂, and n₃; and nuclear angular momentum quantum numbers â â ¤ kε^-3/4 for k > 0. Here the small parameter ε is the fourth root of the ratio of the electron mass to an average nuclear mass.
Master of Science

The ground state electron wavefunction of some molecules has a non-zero angular momentum about the internuclear axis. Molecular rotational momentum can couple with this angular momentum, splitting the energy degeneracy of the two directions of motion about the internuclear axis. Performing a Born-Oppenheimer approximation of such a system will break the relevant energy degeneracy at eighth order. This degeneracy breaking is known as L-doubling.
Master of Science

La prédiction de propriétés spectroscopiques moléculaires et l’interprétation de spectres expérimentaux nécessitent de faire appel à la théorie. Une première étape consiste à se limiter à la spectroscopie électronique dans l’approximation de Born-Oppenheimer ce qui consiste à considérer les noyaux de la molécule comme étant fixes et les états électroniques indépendants les uns des autres. L’objectif de cette thèse est d’étudier la structure électronique de petites molécules organiques et organométalliques dans l’approximation de Born-Oppenheimer dans un premier temps avant d’aller au delà en prenant en compte des effets tels que le couplage vibronique ou le couplage spin-orbite entre les états électroniques. Le premier chapitre est consacré aux méthodes ab initio utilisées pour obtenir les résultats présentés dans les chapitres ultérieurs. Une première partie est consacrée aux méthodes de structure électronique dans l’approximation de Born-Oppenheimer, elle est suivie d’une partie qui traite des effets de couplage vibronique et spin-orbite. Le second chapitre présente une étude de la structure électronique et des courbes d’énergie potentielle des carbènes de métaux de transition MCH+2 (M=Fe, Co, Ni). Le troisième chapitre rapporte les spectres vibroniques des fluoroéthylènes obtenus par simulation et comparés aux spectres expérimentaux afin d’identifier l’origine de différentes contributions spectroscopiques. Enfin le dernier chapitre traite des effets spin-orbite dans l’eau et ses homologues lourds (H2X avec X=O, Te, Po)
Theory is sometime necessary to predict molecular spectroscopic properties and interpret experimental spectra. A first step study can be limited to the electronic spectroscopy in Born-Oppenheimer approximation which consists in considering nuclei fixed and electronic states independent from each other. The scope of this thesis is to first study the electronic structure of small organic and orgnometallic molecules in the Born-Oppenheimer approximation and ultimatly go beyond by taking into account effects such as vibronic or spin-orbit couplings between electronic states. The first chapter is dedicated to the ab initio methods used to obtain the results presented in the following chapters. Electronic structure methods in the Born-Oppenheimer approximation are first presented followed by the methods that treat vibronic and spin-orbit couplings. The second chapter is a study of the electronic structure and potential energy curves of MCH+2 (M=Fe, Co, Ni) transition metal carbenes. Chapter three reports simulated vibronic spectra of fluoroethylenes, they are compared to experimental spectra to indentify the origin of the different spectroscopic contributions. A last chapter deals with the spin-orbit effects in water and its heavy homologous (H2X with X=O, Te, Po)

The fully quantum mechanical 'direct-potential-fit' (DPF) method has become increasingly widely used in the reduction of diatomic spectra. The central problem of this method is the representation of the potential energy and Born-Oppenheimer breakdown (BOB) correction functions. There are a number of problems associated with the existing method and potential forms. This thesis delineates these problems and finds solutions to some of them. In particular, it is shown that use of a different expansion variable and a new treatment of some of the expansions resolves most of the problems. These techniques have been successfully tested on the ground electronic states of the coinage metal hydrides and the Rb2 molecule. To address the problem of representing 'barrier' potential curves, a flexible new functional form, the 'double-exponential long-range' (DELR) potential function, is introduced and applied to the B barrier state of Li2. In addition, the Lambda-doubling level splitting which occurs for singlet Pi electronic states has been taken into account by extending the effective Schrodinger equation. The computer program DSPotFit developed in our laboratory for performing DPF analyses has been extended to incorporate the ability to fit the analytical potential energy functions to tunneling predissociation line widths for quasibound levels. Finally, an attempt is made to investigate whether there exists a hump in the ground state rotationless potential curve of beryllium hydride.

Environ 3% des antiprotons ($$p) stoppes dans l'helium survivent plusieurs microsecondes, contre quelques picosecondes dans tout autre materiau. Cette metastabilite inhabituelle resulte d'une capture sur des etats lies de l'atome exotique $$phe +, denomme atomcule car il s'apparente a la fois a un atome de rydberg quasi-circulaire quasi-classique de grand moment angulaire l n 1 37 et a une molecule diatomique composee d'un noyau charge negativement et caracterisee par une forte excitation rotationnelle j = l. En dehors de cette structure duale originale accessible par spectroscopie laser, la physico-chimie de leur interaction avec d'autres atomes ou molecules a fait l'objet d'etudes microscopiques. Alors que les atomcules resistent a des millions de collisions dans l'helium pur, des contaminants moleculaires comme h 2 les detruisent immediatement, y compris a basse temperature. Dans le cadre born-oppenheimer, nous interpretons l'interaction moleculaire, calculee par des techniques de chimie quantique ab initio, en termes de chemins reactifs classiques, qui presentent des barrieres d'activation compatibles avec celles mesurees dans he et h 2. Nous montrons par une approche monte carlo de trajectoires classiques que la thermalisation detruit fortement les populations initiales, portant la fraction estimee des etats de capture a 3%. Nous etudions aussi la recombinaison dissociative $$phe + + e +e dans une approche de trajectoires classiques pour les noyaux : nous predisons la synthese d'antihydrogene avec un rapport de branchement de 10%, ainsi qu'une nouvelle classe d'atomcules metastables (, $$p, e +, 2e ), qui pourrait etre confirmee par spectroscopie. Ce travail illustre la transferabilite des concepts de chimie physique a l'etude de processus exotiques en presence d'antimatiere, et apporte un eclairage nouveau sur la physico-chimie des radicaux interstellaires froids.

Ce mémoire traite de la dynamique des molécules envisageant une description classique pour les noyaux et quantique pour la structure électronique. Les approches "Born-Oppenheimer" et "Car-Parrinello" sont discutées et un nouvel algorithme est présenté puis validé de par la bonne conservation de l'énergie totale au cours du temps. Il est ensuiote étendu pour simuler l'ensemble canonique et appliqué à la détermination de caractéristiques spectroscopiques de systèmes moléculaires. L'estimation de quantités, telle l'énergie libre, est considérée à l'aide de la théorie de l'ensemble "blue-moon". Cette méthode est appliquée à deux réactions chimiques, mettant en évidence la mise en défaut de l'approche traditionnelle basée sur l'approximation harmonique. Enfin, l'estimation de l'énergie de point zéro au delà de cette approximation est abordée.

Le développement des sources XUV intenses du type laser à électrons libres (LEL) et génération d’harmoniques d’ordre élevé (GHOE) en régime femtoseconde (fs) et sub-fs permet l’investigation des processus non-linéaires ultra rapides dansl’interaction laser-matière. Dans le contexte de l’étude de la dynamique de la photoionisation moléculaire aux temps ultra-brefs, la résolution directe de l’équation de Schrödinger dépendante du temps (ESDT) s’est révélée cruciale pour l’interprétationdes observations expérimentales. Dans cette thèse, nous présentons des calculs ab-initio pour la photo-ionisation de H2 en impulsion ultra-brève UV et X. On s’intéressera plus particulièrement aux processus non-linéaires impliquant deux photons,à leur rôle dans le couplage dynamique électron-noyaux ainsi qu’aux effets liés aux corrections à l’approximation dipolaire (AD).Notre approche théorique est basée sur la méthode spectrale, elle nécessite la détermination des états quantiques de la molécule isolée. Ces états sont calculés dans l’approximation Born-Oppenheimer (BO) dans le contexte de la méthode d’interaction de configuration, en s’appuyant sur la théorie des collisions pour traiter les continua et sur le formalisme de Feshbach pour calculer les états autoionisants. Dans le traitement de l’interaction avec le rayonnement, nous nous basons sur un développement multipolaire du vecteur potentiel du champ en jauge de Coulomb, dont nous conservons les termes correspondant à l’AD et aux effets de retard jusqu’à l’ordre O(1/c). Finalement, nous utilisons des approches perturbatives et nonperturbatives pour obtenir l’amplitude de transition liée à l’ionisation, à partir de laquelle on calcule les sections efficaces, les spectres de photoélectrons et les distributionsangulaire dans le référentiel de la molécule [...]
The development of intense XUV sources through free-electron lasers (FELs) and high-order harmonic generation (HHG) in the femtosecond (fs) and sub-fs domains provides a unique tool to investigate non-linear ultrafast laser-matter interaction. In the study of the dynamics of molecular photoionization at ultrashort timescales, the Time-Dependent Schrödinger Equation (TDSE) has been crucial for the interpretation of experimental observations. In this thesis, we present results for ab initio calculations of H2 photoionization with UV/X-ray ultrashort laser pulses. We focus on the study of non-linear processes involving two photons and their role in the coupled electron-nuclear dynamics they induce and their study beyond the dipole approximation (DA). Our theoretical approach is based on a spectral method, which requires determining the quantum states of the field-free molecule. These states are calculated in the Born-Oppenheimer approximation employing a configuration interaction scheme together with multichannel scattering theory to determine for the treatment of continuum states, and the Feshbach partitioning formalism to account for autoionization. We resort to a multipolar expansion of the vector potential in the Coulomb gauge, from which we keep the terms corresponding to DA and retardation effects up to O(1/c), to account for the interaction with radiation. Finally, we make use of perturbative and non-perturbative propagation schemes to obtain transition amplitudes from which we can extract cross-sections, photoelectron spectra (PES), and molecular frame angular distributions (MFPADs).In the first part of the results, we demonstrate the coherent control of ionization and dissociation achieved by filtering the higher harmonics in an attosecond pulse train (APT) in an XUV pump-UV probe scheme. By solving the TDSE in DA including electronic and nuclear motion, we are able to extract nuclear and electronic kinetic energy release (KER) spectra to analyze the main ionization pathways as afunction of the delay between pump and probe. We then discuss the effect of harmonic filtering in manipulating one-photon against two-photon ionization yields, dissociative ionization channels, and asymmetries in the MFPADs. In the second part of the results of the thesis, we report the first calculations of Stimulated Raman Scattering (SRS) and Stimulated Compton Scattering (SCS) in H2 with intense X-ray laser fields. These non-linear phenomena consist in the absorption of a photon and the subsequent stimulated emission of a less energetic one leaving the molecule in an excited state (SRS) or effectively ionizing it (SCS). Theoretically, the inclusion of effects beyond DA becomes mandatory. We begin by investigating the relative role of the dipole (A.P) and non-dipole (A2) interaction terms through a perturbative study of the Raman cross-section. The role of the high energy electronic continuum in the partial cancellation of the dipole contribution is also analyzed. We then present results from SRS and SCS calculations using ultra-short pulses in which we compare the relative contribution of the dipole and non-dipole routes as a function of the photon energy. We assert the validity of perturbation theory by directly comparing SRS calculations with results obtained by solving the TDSE. In SCS, the interference between dipole and non-dipole routesproduces asymmetries in the MFPADs, which we analyze. Special attention is givento the effect of molecular orientation.Finally, we study SCS with two colors, focusing on the effect of the angle between the pulse propagation directions. As seen in atoms, non-dipole effects are enhanced for counter-propagating pulses. We also investigate the effect of color separation in energy

Ce travail s'inscrit dans le cadre de l'analyse des transitions non-adiabatiques pour les hamiltoniens des molécules diatomiques. Nous considérons ainsi l'étude semi-classique d'un système de deux équations de Schrödinger couplées dont les valeurs propres du symbole matriciel ont un croisement évité (ici de codimension 2) non dégénéré avec un gap d'ordre racine carrée du paramètre semi-classique. Ce régime particulier est caractérisé par des transitions non-adiabatiques qui ne sont pas exponentiellement faibles. Nous montrons qu'il existe un développement asymptotique complet, dont le premier terme (purement géométrique) est donne par la formule de Landau-Zener, décrivant la transition pour les amplitudes. Pour cela nous déduisons du système d'équations, une équation pour une seule des deux composantes ou le couplage intervient comme symbole sous-principal. Localement près du point de croisement, cet operateur pseudo-différentiel se ramène à une forme normale exactement soluble (celle que l'on retrouve pour l'étude de l'équilibre instable) et qui permet, avec la conservation du wronskien, de décrire la matrice de transfert entre les solutions BKW (adiabatiques) définies loin du point de croisement. Nous utilisons ainsi la théorie mathématique de l'analyse semi-classique dont la première partie de ce travail cherche a donner une introduction relativement détaillée qui peut être lue indépendamment.