Sur la performance des approches des sous-systèmes pour la modélisation les espèces contenant des éléments lourds dans les solutions

On the performance of subsystem approaches to model heavy element species in solution

• Auteur / Autrice : Yassine Bouchafra
• Direction : André Severo Pereira Gomes, Valérie Vallet
• Type : Thèse de doctorat
• Discipline(s) : Milieux dilués et optique fondamentale
• Date : Soutenance le 25/09/2019
• Etablissement(s) : Université de Lille (2018-2021)
• Ecole(s) doctorale(s) : École doctorale Sciences de la matière, du rayonnement et de l'environnement (Villeneuve d'Ascq, Nord)
• Partenaire(s) de recherche : Laboratoire : Laboratoire de Physique des Lasers, Atomes et Molécules (PhLAM)

Mots clés

Mots clés contrôlés

Solvatation

Éléments lourds

Effets relativistes

Ionisation

Spectroscopie de photoélectrons

Spectroscopie de la résonance magnétique nucléaire

Théorie de la fonctionnelle de densité

Fonctions d'onde

Théorie quantique

Mots clés libres

Systèmes moléculaires

Approches des sous-systèmes

Résumé

Afin de comprendre les mesures spectroscopiques, il est d'une grande importance de comprendre les processus physiques au niveau microscopique à cause du rôle des électrons (et des noyaux) dans le système. Le traitement de ces particules nécessite, au moins, un niveau de mécanique quantique pour le système d'intérêt. La présence des éléments lourds dans le système aggrave la situation à cause de l'obligation de tenir en compte, en plus du grand nombre de particules, les effets relativistes. Après un premier chapitre sur les différentes méthodes théorique, le second chapitre explore les méthodes d'embedding qui peuvent apporter des solution dans le cas où un traitement quantique pour tout le système est demandé. La suite de ce travail concentre sur l'exploration de la performance de la méthode Frozen Density Embedding dans la description des propriétés électroniques (Potentiels d'ionisation des halogénures solvatés ) dans les chapitres 3 et 4 et des propriétés magnétiques (Écrantage RMN et couplage J) dans le chapitre 5.

In order to understand spectroscopic measurements, it is important to understand the physical processes taking place at a microscopic scale, since these are related to the behaviour of the electrons (and nuclei) in the system. The treatment of such particles requires one way or another a quantum mechanical treatment of the atoms and molecules that make up a given system of interest. This means that in order to achieve that we must perform theoretical sim- ulations and, if such systems contain heavy elements, this is a particularly dicult task, since we not only have to deal with the large number of particles but also include relativistic e↵ects. These diculties have motivated the development of several theoretical approaches that sim- plify the treatment of at least part of the total system. This thesis investigates the use of the Frozen Density Embedding (FDE) approach to the calculation of molecular properties of complex systems. FDE is a formally exact method with which we can separate a complex molecular system into subsystems and choose the most suit- able electronic structure approach to treat each of these. With this separation, we can focus the computational e↵ort into one or a few subsystems of interest and treat them very accurately with relativistic electronic structure methods that include spin-orbit coupling, while the e↵ect of the remaining subsystems (environment) on the system of interest is treated at a suciently high level of accuracy. Our first interest was in the quantum mechanical description of ionisation energies for molecular aggregates of microsolvated halides, such as found in water droplets. We have ex- plored the sensitivity of these energies to structural changes around the halides and among the waters, and how these energies evolve with the size of the aggregate, with our results being in quantitative agreement with experimental data, and we have predicted the ionisation energies of the heaviest of halides, astatide, which is of interest as a radiotherapeutic agent. Our results demonstrate that with the combination of relativistic EOM-CC for the active subsystem and DFT for the environment, a↵orded by FDE, one can rival with quite sophisticated theoretical approaches based on periodic quasi-particle calculations which are the current state-of-the-art for condensed matter simulations. We have also explored the performance of FDE for the description of solvent e↵ects on magnetic properties (indirect spin-spin couplings and NMR shielding tensors) for a complex PtTl(CN)5 containing a metal-metal bond between the heavy centres (Pt, Tl), this time purely at relativistic DFT level. For spin-spin couplings, we have shown that much like prior theoretical results, we require an extensive first hydration shell around the complex, but nevertheless arrive at a semi-quantitative agreement with experiment. For NMR shieldings on the other hand, FDE allows us to significantly reduce the amount of water molecules explicitly added to the active subsystem to the first hydration shell around the Tl atom. This might open up the perspective to employing FDE with more accurate with more accurate electronic structure methods for this property for this class of compounds.