Le réacteur ITER exploitera trois types de chauffage : injection de neutres (NBI), chauffages ohmique et haute fréquence. Les sources NBI utilisent un jet d'atomes d'hydrogène et de deutérium. La région du conducteur à l'intérieur de la bobine radiofréquence produits des ions hydrogènes par des collisions avec des électrons chauds. Les ions sont extraits par le champ électrique dans la région d'expansion où le césium évaporé entre dans le plasma. Celui-ci entre alors dans la région d'extraction où les atomes, les ions et les molécules d'hydrogène sont convertis en ions négatifs sur une grille recouverte de césium. La chimie de ces processus est plutôt compliquée et n'est pas très bien comprise. Le but de ce travail est d'examiner la majorité des processus qui pourraient avoir un impact sur les espèces anioniques hydrogénées soit par des réactions de formation ou destruction liées au césium. La réactivité du césium, la dynamique de CsH ainsi que celles d'espèces chimiques associées à CsH peuvent être bien décrites aujourd'hui en utilisant des méthodes ab initio. Les méthodes CASSCF et CASPT2 ont été employées pour calculer les courbes d'énergie potentielle de CsH et CsH+ dans leurs états fondamentaux et excités afin d'estimer leurs constantes spectroscopiques et obtenir les représentations des orbitales moléculaires de CsH et de ses ions. Les énergies de réactions ont été également déterminées pour plusieurs espèces chimiques de type CsxHy associées à CsH en utilisant la méthode CCSD(T). L'ensemble des résultats obtenus dans cette thèse permet de mieux comprendre les faits expérimentaux et ainsi de mieux caractériser la chimie de ces processus. / The ITER reactor will exploit three types of heating: neutral beam injection (NBI), ohmic heating, and high frequency heating. NBI sources utilize the jet of accelerated H/D atoms. The driver region inside radio-frequency coil produces hydrogen ions by collisions with hot electrons. Ions are extracted by electric field to expansion region where the evaporated caesium enters the plasma. Plasma then enters extraction region where the atoms, ions and molecules of hydrogen are converted to negative ions on a grid that is being covered with caesium to lower its work function. Chemistry of these processes is rather complicated and not well understood. The goal of this work is to investigate the majority of processes which might have impact on hydrogen anions in either formative or destructive way associated with caesium. Reactivity of caesium, caesium hydride dynamics and geometries of chemical species associated with caesium hydride can be well described using ab initio methods. We have used CASSCF and CASPT2 methods to calculate the potential energy curves of CsH and CsH+ in their ground and excited states, to model their spectroscopy and to analyse the orbital picture of caesium hydride and its ions. We have also calculated the reaction energies of several chemical species CsxHy associated with caesium hydride and applied the CCSD(T) method to calculate the potential curves and precise reaction energies. Altogether our results bring deeper insight into the experimental data and change the understanding of these processes.

Transition-metal based molecules and point defects in wide-bandgap semiconductors have been of particular interest lately due to their potential quantum information science applications. To accurately calculate the electronic properties of these systems from first principles, it is important to appropriately account for electronic correlation effects. Density functional theory (DFT) has been one of the most popular methods to perform calculations on correlated systems, due to the combination of numerical efficiency and precision in many applications. However, traditional DFT methods fail to accurately calculate the important electronic and magnetic properties, such as bandgaps in semiconductors or magnetic ordering in defects, to name a few. This dissertation focuses on two areas in which traditional DFT methods are likely to produce inaccurate predictions. The first area is connected to an error that is intrinsic to most DFT formulations due to the approximate nature of the exchange-correlation functional, known as the self-interaction error (SIE). It is known to cause the underestimation of bandgaps in solids, underestimated reaction barriers in molecules, and incorrect dissociation curves. The second area is the case where the ground and/or excited states are described by multiconfigurational wavefunctions rather than a single Slater determinant. Chapter 1 of the thesis provides a brief overview of various electronic-structure methods, as well as the Fermi-Löwdin Orbital Self-Interaction Correction method (FLOSIC) which is used to remedy the SIE in DFT. Chapter 2 reports on the application of the FLOSIC-DFT on a Cu-based molecule, and its effects on the predicted electronic properties. Chapter 3 describes the application of the FLOSIC-DFT to the computation of the hyperfine coupling terms, which are crucial for the realization of spin qubits and for interpreting electron paramagnetic resonance experiments. Chapter 4 turns to the application of a multiconfigurational method to describe the electronic properties of a silicon vacancy in silicon carbide, a potential point-defect qubit. / Doctor of Philosophy / Computational electronic structure methods, which attempt to predict optical, electronic, and other properties of molecules and materials just by solving the Schrödinger equation for the wavefunction of the electrons in them, have been instrumental in many areas of research, including the design of semiconductors, drug discovery, improved solar panel design, and discovering systems that can work as qubits for quantum-computing purposes, to name a few. One of the most successful sets of these methods, known as Density Functional Theory (DFT) methods, makes solving for electronic wavefunctions (and from them, other materials properties) computationally efficient, while maintaining the accuracy of such predictions by accounting for the complex quantum-mechanical interactions between the particles. For this, DFT was the subject of the 1998 Nobel Prize in chemistry. However, there are several areas where DFT is typically not successful in producing accurate predictions. One of the areas is connected to the approximated term in all DFT methods that often erroneously accounts for electrons interacting on themselves (an effect known as the self-interaction error). The other area is related to systems that must be described with superposition of several electronic configurations. Chapter 1 of the thesis provides a brief overview of various electronic-structure methods, as well as the Fermi-Löwdin Orbital Self-Interaction Correction method (FLOSIC) which suggests a modification to the standard DFT methods that aims to remove the self-interaction error. Chapter 2 reports on the application of the FLOSIC-DFT on a Cu-based molecule, and its effects on the predicted electronic properties. Chapter 3 describes the application of the FLOSIC-DFT to describe the interaction between the magnetic moments of electrons and nuclei, known as the hyperfine coupling, which is crucial for the realization of spin qubits and for interpreting some experimental results. Chapter 4 turns to the application of a multiconfigurational method to describe the electronic properties of a silicon vacancy in silicon carbide, a potential point-defect qubit.

Aquest treball teòric estudia l'acoblament magnètic en complexos bi- i trinuclears heterometàl·lics amb lligands pont oxamido, oxamato, ditiooxalato i anàlegs. Per calcular la seva estructura electrònica s'han usat mètodes multireferencials, en particular diferents variants del mètode DDCI, desenvolupat en el grup, i el mètode CASPT2. Per diferents sistemes binuclears coneguts de Cu(II) i Mn(II), l'acoblament magnètic i els mapes de densitat de spin calculats reprodueixen acuradament les dades experimentals. L'acoblament antiferromagnètic en aquests depèn de la transferència de càrrega del lligand al metall, lligada a l'electronegativitat dels àtoms coordinats. En els sistemes hipotètics de tipus Cu(II)-M(II)-Cu(II), on M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu i Zn, la magnitud de l'acoblament estimada depèn de l'electronegativitat del metall central, anant de feblement ferromagnètic pel Sc a moderadament antiferromagnètic pel Cu. Aquest treball aporta la interpretació microscòpica de l'acoblament en aquests sistemes, així com la validació i/o les limitacions dels mètodes de càlcul emprats. / This theoretical work examines the magnetic coupling in bi- and trinuclear heterometallic transition metal complexes with bridging ligands such as oxamido, oxamato, ditiooxalato and analogues. To calculate their electronic structure multireference methods have been used, including different variants of DDCI method, developed in our group, and CASPT2 method. For different Cu(II)-Mn(II) binuclear known systems, the magnetic couplings and spin density maps calculated accurately reproduce the experimental data. The antiferromagnetic coupling in these compounds depends on the charge transfer from ligand to metal, linked to the electronegativity of coordinated atoms. In the hypothetical systems of type Cu(II)-M(II)-Cu(II), where M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, the magnitude of the estimated coupling depends on the electronegativity of the metal core, going from the weakly ferromagnetic for Sc to moderately antiferromagnetic for Cu. This work provides the microscopic interpretation of the coupling in these systems, as well as the validation and/or limitations of the computational methods used.

Dans cette thèse, les propriétés optiques de biomolécules importantes ont été étudiées en utilisant une approche théorique et, dans un cas, aussi expérimentale. La Théorie de la fonctionnelle de la densité (DFT) et la timedependent-DFT (TD-DFT) sont les principales méthodes de chimie quantique utilisées dans cette thèse. Plusieurs spectroscopies ont été étudiées (au niveau théorique et, dans certains cas, également au niveau expérimental) : absorption électronique linéaire (absorption à un photon, OPA) et non-linéaire (absorption à deux ou trois photons, TPA et 3PA), dichroïsme circulaire électronique (DCE) et spectroscopie de fluorescence. Les effets de l’environnement, particulièrement importants dans des systèmes biologiques, ont été pris en compte, pour les propriétés de l’état fondamental et des états excités en utilisant une méthode multi-échelles QM/MM appelée Polarizable Embedding (PE). L’échantillonnage des conformations a été pris en compte avec des simulations de dynamique moléculaire (MD) qui sont basées sur la mécanique classique. Deux thématiques ont été étudiées dans cette thèse : le cholestérol et le design in silico de ses analogues fluorescents ainsi que la caractérisation des coudes de type β dans différentes conformations grâce à la simulation des spectres DCE. La simulation de plus d’une spectroscopie a été importante dans l’étude des états excités du cholestérol dans des solutions organiques. Le design in silico a suggéré un nouveau stérol-polyénique (P-stérol) qui montre despropriétés optiques améliorées pour le mécanisme d’excitation à trois photons par rapport au déhydroergostérol (DHE), une sonde du cholestérol déjà très utilisée. Ce nouveau P-stérol a été suggéré pour la synthèse. L’étude des spectres de DCE des coudes β en différentes conformations a mené une double conclusion : même si deux allures de DCE pour les conformations des coudes β étudiées (4) ont été trouvées (dans la majorité des cas), la spectroscopie de DCE doit toujours être associée à d’autres techniques spectroscopiques dans la caractérisation en solution des coudes β. / In this thesis, the optical properties of important biomolecules were studied using a theoretical approach and, in one case, also an experimental one. Density Functional Theory (DFT) and time-dependent-DFT (TD-DFT), were the principal quantum chemical methods adopted in this thesis.Various spectroscopies were studied (theoretically and, in some cases, also experimentally) : linear (one-photon, OPA) and non-linear (two- and three-photon, TPA and 3PA) electronic absorption, electronic circular dichroism (ECD) and fluorescence spectroscopy. The environment effects, which are particularly important in biological systems, were taken into account, for both ground and excited states properties, using a multiscale QM/MM method called Polarizable Embedding (PE). The sampling of conformations was addressed by Molecular Dynamic (MD) simulations based on classical mechanics. Two topics were studied in this thesis: cholesterol and the in-silico design of its fluorescent analogues, and the characterization of β-turns in different conformations by simulations of their ECD spectra in aqueous solutions. The simulation of more than one spectroscopy resulted to be important when studying the electronic excited states of cholesterol in organic solutions. The in-silico design study suggested a novel polyene-sterol (P-sterol) which shows improved optical properties for the three-photon excitation mechanism with respect to dehydroergosterol (DHE), an already widely used cholesterol probe. This new P-sterol was thus suggested for synthesis. The achievement from the study of ECD spectra for different β-turn conformations is two-fold: even if two ECD patterns for the β-turn conformations studied (4) were found (in most of cases), ECD spectroscopy should be always associated with other spectroscopic techniques when trying to characterize the β-turn conformations in solutions.

Title: Theoretical study of spin-orbit coupling on spectra and photophysics of rhenium complexes Author: RNDr. Radka Heydová Department: Physical and Macromolecular Chemistry Supervisor: Ing. Stanislav Záliš, CSc., JHI AS CR, v.v.i. Supervisor's e-mail address: stanislav.zalis@jh.inst-cas.cz Abstract: Relativistic effects, especially spin-orbit coupling (SOC), play an essential role in transition metal chemistry and SOC treatment is indispensable for a correct theoretical description. To demonstrate the importance of SOC, the energies and oscillator strengths of vertical transitions for a series of [ReX(CO)3(2,2'-bipyridine)] (X = Cl, Br, I) and [Re(imidazole)(CO)3(1,10-phenanthroline)]+ complexes were calculated in the spin-free (SF) and spin-orbit (SO) conceptual frameworks. Two different computational approaches were adopted: SO-MS-CASPT2 where SOC was added a posteriori using a configuration interaction model (SO-RASSI), and the approximate perturbative SO-TD-DFT method. Relativistic effects were included via the two-component Douglas-Kroll-Hess transformation and the zeroth-order regular approximation in the former and the latter technique, respectively. The SF (i.e. accounting only for the scalar relativistic effects) and SO results from both methods were compared with each other and to available...