Ce travail présente la mesure des polarisabilités généralisées (GPs) électrique αE(Q2) et magnétique βM(Q2) du proton à Q2 =0.2 GeV 2. Les GPs sont définies dans le contexte de la diffusion Compton virtuelle (VCS), γ*p → γp, où Q2 est le quadri-moment de transfert du photon virtuel. Les GPs sont la généralisation des polarisabilités mesurées en diffusion Compton réel (RCS) en considérant leur dépendance en Q2. Ce sont des propriétés dynamiques du proton définissant sa déformation lorsqu'un champ électromagnétique lui est appliqué. αE(Q2) (ou βM(Q2)) donne accès à la densité de polarisation (magnétisation) locale du proton déformé. L'effet des GPs ne contribuant qu'à 1 – 15 % de la section efficace ep → epγ une mesure de haute précision est requise. Ce travail s'inscrit dans le cadre d'une expérience conduite par la collaboration A1 de MAMI à trois valeurs inédites de Q2 : 0.1,0.2 et 0.45 GeV 2. L'analyse de premier niveau comporte une calibration détaillée des données expérimentales et l'utilisation d'une simulation de l'expérience. L'extraction des GPs requiert la mesure et la renormalisation des sections efficaces ep → epγ et la correction des effets radiatifs. Les résultats obtenus par le fit « LEX » et « DR » sont en très bon accord. / This work presents the measurement of the generalized electric αE(Q2) and magnetic βM(Q2) polarisabilities (GPs) of the proton. The GPs are defined in the Virtual Compton Scattering (VCS) context, i.e. the reaction γ*p → γp where Q2 is the four-momentum transfer of the virtual photon. The GPs are a generalization of polarizabilities measured in real Compton scattering (RCS) by taking into account the Q2-dependency. They are dynamical properties of the proton when it is deformed by an applied electromagnetic fiels. αE(Q2) (or βM(Q2)) gives access to the local polarization (or magnetization) density of the deformed proton. The studied VCS process is accessible by the photon-electroproduction reaction (ep → epγ). The GP effect is a 1 – 15 % contribution to the ep → epγ cross section, requiring a high-precision mleasurement. The present work is a part of an experiment conducted by the A1 collaboration at MAMI at three new Q2 values : 0.1,0.2 and 0.45 GeV 2. This thesis details the extraction at 0.2 GeV 2. The experiment uses the 1 GeV electron beam, the 5 cm liquid hydrogen target and spectrometers A (B) to detect the final electron (proton). The first-level analysis includes a detailed calibration of experimental data, and the use of a simulation of the experiment. The measurement of the unpolarized ep → epγ cross section is described with two of its important features : the correction of the radiative effects and the renormalization. Two differents frameworks are used to extract the GPs : the Low Energy Theorem (LET) and the dispersion relation model (DR). The two extractions lead to results in good argument. The world data still raises question about the Q2-behavior of the Gps.

<p>In this thesis, we present novel computational methods and frameworks to address the challenges associated with the determination of free energy profiles for condensed-phase chemical reactions using combined quantum mechanical and molecular mechanical (QM/MM) approaches. We focus on overcoming issues related to force matching, molecular polarizability, and convergence of free energy profiles. First, we introduce a method called Reaction Path-Force Matching in Collective Variables (RP-FM-CV) that efficiently carries out ab initio QM/MM free energy simulations through mean force fitting. This method provides accurate and robust simulations of solution-phase chemical reactions by significantly reducing deviations on the collective variables forces, thereby bringing simulated free energy profiles closer to experimental and benchmark AI/MM results. Second, we explore the role of pairwise repulsive correcting potentials in generating converged free energy profiles for chemical reactions using QM/MM simulations. We develop a free energy correcting model that sheds light on the behavior of repulsive pairwise potentials with large force deviations in collective variables. Our findings contribute to a deeper understanding of force matching models, paving the way for more accurate predictions of free energy profiles in chemical reactions. Next, we address the underpolarization problem in semiempirical (SE) molecular orbital methods by introducing a hybrid framework called doubly polarized QM/MM (dp-QM/MM). This framework improves the response property of SE/MM methods through high-level molecular polarizability fitting using machine learning (ML)-derived corrective polarizabilities, referred to as chaperone polarizabilities. We demonstrate the effectiveness of the dp-QM/MM method in simulating the Menshutkin reaction in water, showing that ML chaperones significantly reduce the error in solute molecular polarizability, bringing simulated free energy profiles closer to experimental results. In summary, this thesis presents a series of novel methods and frameworks that improve the accuracy and reliability of free energy profile estimations in condensed-phase chemical reactions using QM/MM simulations. By addressing the challenges of force matching, molecular polarizability, and convergence, these advancements have the potential to impact various fields, including computational chemistry, materials science, and drug design.</p>

Indiana University-Purdue University Indianapolis (IUPUI) / In this thesis, we present novel computational methods and frameworks to address the challenges associated with the determination of free energy profiles for condensed-phase chemical reactions using combined quantum mechanical and molecular mechanical (QM/MM) approaches. We focus on overcoming issues related to force matching, molecular polarizability, and convergence of free energy profiles. First, we introduce a method called Reaction Path-Force Matching in Collective Variables (RP-FM-CV) that efficiently carries out ab initio QM/MM free energy simulations through mean force fitting. This method provides accurate and robust simulations of solution-phase chemical reactions by significantly reducing deviations on the collective variables forces, thereby bringing simulated free energy profiles closer to experimental and benchmark AI/MM results. Second, we explore the role of pairwise repulsive correcting potentials in generating converged free energy profiles for chemical reactions using QM/MM simulations. We develop a free energy correcting model that sheds light on the behavior of repulsive pairwise potentials with large force deviations in collective variables. Our findings contribute to a deeper understanding of force matching models, paving the way for more accurate predictions of free energy profiles in chemical reactions. Next, we address the underpolarization problem in semiempirical (SE) molecular orbital methods by introducing a hybrid framework called doubly polarized QM/MM (dp-QM/MM). This framework improves the response property of SE/MM methods through high-level molecular polarizability fitting using machine learning (ML)-derived corrective polarizabilities, referred to as chaperone polarizabilities. We demonstrate the effectiveness of the dp-QM/MM method in simulating the Menshutkin reaction in water, showing that ML chaperones significantly reduce the error in solute molecular polarizability, bringing simulated free energy profiles closer to experimental results. In summary, this thesis presents a series of novel methods and frameworks that improve the accuracy and reliability of free energy profile estimations in condensed-phase chemical reactions using QM/MM simulations. By addressing the challenges of force matching, molecular polarizability, and convergence, these advancements have the potential to impact various fields, including computational chemistry, materials science, and drug design.