This thesis consists of a summary and four scientific articles. All four articles consider various aspects of stochastic differential equations and the purpose of the summary is to provide an introduction to this subject and to supply the notions required in order to fully understand the articles. In the first article we conduct a thorough study of the multi-dimensional Skorohod problem in time-dependent domains. In particular we prove the existence of cádlág solutions to the Skorohod problem with oblique reflection in time-independent domains with corners. We use this existence result to construct weak solutions to stochastic differential equations with oblique reflection in time-dependent domains. In the process of obtaining these results we also establish convergence results for sequences of solutions to the Skorohod problem and a number of estimates for solutions, with bounded jumps, to the Skorohod problem. The second article considers the problem of determining the sensitivities of a solution to a second order parabolic partial differential equation with respect to perturbations in the parameters of the equation. We derive an approximate representation of the sensitivities and an estimate of the discretization error arising in the sensitivity approximation. We apply these theoretical results to the problem of determining the sensitivities of the price of European swaptions in a LIBOR market model with respect to perturbations in the volatility structure (the so-called ‘Greeks’). The third article treats stopped diffusions in time-dependent graph domains with low regularity. We compare, numerically, the performance of one adaptive and three non-adaptive numerical methods with respect to order of convergence, efficiency and stability. In particular we investigate if the performance of the algorithms can be improved by a transformation which increases the regularity of the domain but, at the same time, reduces the regularity of the parameters of the diffusion. In the fourth article we use the existence results obtained in Article I to construct a projected Euler scheme for weak approximation of stochastic differential equations with oblique reflection in time-dependent domains. We prove theoretically that the order of convergence of the proposed algorithm is 1/2 and conduct numerical simulations which support this claim.

Cette thèse étudie une approche intégrant la gestion de l’horaire et la conception de réseaux de services pour le transport ferroviaire de marchandises. Le transport par rail s’articule autour d’une structure à deux niveaux de consolidation où l’affectation des wagons aux blocs ainsi que des blocs aux services représentent des décisions qui complexifient grandement la gestion des opérations. Dans cette thèse, les deux processus de consolidation ainsi que l’horaire d’exploitation sont étudiés simultanément. La résolution de ce problème permet d’identifier un plan d’exploitation rentable comprenant les politiques de blocage, le routage et l’horaire des trains, de même que l’habillage ainsi que l’affectation du traffic. Afin de décrire les différentes activités ferroviaires au niveau tactique, nous étendons le réseau physique et construisons une structure de réseau espace-temps comprenant trois couches dans lequel la dimension liée au temps prend en considération les impacts temporels sur les opérations. De plus, les opérations relatives aux trains, blocs et wagons sont décrites par différentes couches. Sur la base de cette structure de réseau, nous modélisons ce problème de planification ferroviaire comme un problème de conception de réseaux de services. Le modèle proposé se formule comme un programme mathématique en variables mixtes. Ce dernie r s’avère très difficile à résoudre en raison de la grande taille des instances traitées et de sa complexité intrinsèque. Trois versions sont étudiées : le modèle simplifié (comprenant des services directs uniquement), le modèle complet (comprenant des services directs et multi-arrêts), ainsi qu’un modèle complet à très grande échelle. Plusieurs heuristiques sont développées afin d’obtenir de bonnes solutions en des temps de calcul raisonnables. Premièrement, un cas particulier avec services directs est analysé. En considérant une cara ctéristique spécifique du problème de conception de réseaux de services directs nous développons un nouvel algorithme de recherche avec tabous. Un voisinage par cycles est privilégié à cet effet. Celui-ci est basé sur la distribution du flot circulant sur les blocs selon les cycles issus du réseau résiduel. Un algorithme basé sur l’ajustement de pente est développé pour le modèle complet, et nous proposons une nouvelle méthode, appelée recherche ellipsoidale, permettant d’améliorer davantage la qualité de la solution. La recherche ellipsoidale combine les bonnes solutions admissibles générées par l’algorithme d’ajustement de pente, et regroupe les caractéristiques des bonnes solutions afin de créer un problème élite qui est résolu de facon exacte à l’aide d’un logiciel commercial. L’heuristique tire donc avantage de la vitesse de convergence de l’algorithme d’ajustement de pente et de la qualité de solution de la recherche ellipsoidale. Les tests numériques illustrent l’efficacité de l’heuristique proposée. En outre, l’algorithme représente une alternative intéressante afin de résoudre le problème simplifié. Enfin, nous étudions le modèle complet à très grande échelle. Une heuristique hybride est développée en intégrant les idées de l’algorithme précédemment décrit et la génération de colonnes. Nous proposons une nouvelle procédure d’ajustement de pente où, par rapport à l’ancienne, seule l’approximation des couts liés aux services est considérée. La nouvelle approche d’ajustement de pente sépare ainsi les décisions associées aux blocs et aux services afin de fournir une décomposition naturelle du problème. Les résultats numériques obtenus montrent que l’algorithme est en mesure d’identifier des solutions de qualité dans un contexte visant la résolution d’instances réelles. / This thesis studies a scheduled service network design problem for rail freight transportation planning. Rails follow a special two level consolidation organization, and the car-to-block, block-to-service handling procedure complicates daily operations. In this research, the two consolidation processes as well as the operation schedule are considered simultaneously, and by solving this problem, we provide an overall cost-effective operating plan, including blocking policy, train routing, scheduling, make-up policy and traffic distribution. In order to describe various rail operations at the tactical level, we extend the physical network and construct a 3-layer time-space structure, in which the time dimension takes into consideration the temporal impacts on operations. Furthermore, operations on trains, blocks, and cars are described in different layers. Based on this network structure, we model the rail planning problem to a service network design formulation. The proposed model relies on a complex mixed-integer programming formulation. The problem is very hard to solve due to the computational difficulty as well as the tremendous size of the application instances. Three versions of the problem are studied, which are the simplified model (with only non-stop services), complete model (with both non-stop and multi-stop services) and very-large-scale complete model. Heuristic algorithms are developed to provide good feasible solutions in reasonable computing efforts. A special case with non-stop services is first studied. According to a specific characteristic of the direct service network design problem, we develop a tabu search algorithm. The tabu search moves in a cycle-based neighborhood, where flows on blocks are re-distributed according to the cycles in a conceptual residual network. A slope scaling based algorithm is developed for the complete model, and we propose a new method, called ellipsoidal search, to further improve the solution quality. Ellipsoidal search combines the good feasible solutions generated from the slope scaling, and collects the features of good solutions into an elite problem, and solves it with exact solvers. The algorithm thus takes advantage of the convergence speed of slope scaling and solution quality of ellipsoidal search, and is proven effective. The algorithm also presents an alternative for solving the simplified problem. Finally, we work on the very-large-size complete model. A hybrid heuristic is developed by integrating the ideas of previous research with column generation. We propose a new slope scaling scheme where, compared with the previous scheme, only approximate service costs instead of both service and block costs are considered. The new slope scaling scheme thus separates the block decisions and service decisions, and provide a natural decomposition of the problem. Experiments show the algorithm is good to solve real-life size instances.

The resolution of the complex physics of rotating configurations is critical for any engineering analysis that requires multiple frames of reference. Two well-known applications are in the rotorcraft and wind energy industries. Rotor wake impingement from rotor-fuselage and wind turbine-tower interactions impact structural and acoustic characteristics. Additionally, parasite drag resulting from rotorcraft hubs may result in severe limitations on forward flight vehicle performance. Complex turbulent wakes from rotors and hubs impinging on downstream empennage can create adverse aeroelastic behavior and can affect handling qualities. Numerical simulations of these flows require state-of-the-art Navier Stokes methods using dynamic overset grids. However, many current methods typically used in industry result in wakes that dissipate essential features. In order to address these concerns, two advancements are introduced in this thesis. Feature-based grid adaptation on dynamic overset grids has been developed and demonstrated with an unstructured Navier Stokes solver. The unique feature of the adaptation technique is that it is applied globally on the overset grid system except within the boundary layer. In concert with grid adaptation, an efficient parallelized search algorithm for solution interpolation over massively distributed systems has been created. This results in cost-effective interpolation that retains the numerical order of accuracy and has been verified in both space and time. The improvements have been demonstrated for rotor-fuselage interaction and a generic rotating hub. Detailed analysis of convergence of the methodology and sensitivity of the results to relevant parameters have also been included.

The non-adiabatic quantum molecular dynamics (NA-QMD) method couples self-consistently classical nuclear motion with time-dependent density functional theory (TDDFT) in basis expansion for the electron dynamics. It has become a versatile approach to study the dynamics of atoms, molecules and clusters in a wide range of scenarios. This work presents applications of the NA-QMD method to important benchmark systems and its systematic extension to include quantum effects in the nuclear motion. Regarding the first objective, a complete study of the strong-field ionization and dissociation dynamics of nature’s simplest molecule H2+ is performed. By including all electronic and nuclear degrees of freedom and all reaction channels, molecular rotation is shown to play an important role in the ionization process. In addition, strong orientation effects in the energy deposition process of the Buckminster fullerene C60 in short intense laser pulses are surprisingly found in full dimensional calculations. Their consequences on the subsequent nuclear relaxation dynamics shed new light on available experimental data and future experiments are proposed to confirm the detailed predictions. Regarding the second objective, the NA-QMD formalism is basically extended to take electron-nuclear correlations into account. This extension is achieved by means of a trajectory surface hopping scheme in the adiabatic Kohn-Sham framework. First studied examples from collision physics and photochemistry illustrate the relevance and importance of quantum effects in the nuclear dynamics.

The work carried out during this thesis focuses on the quantum dynamics of the diffusion of hydrogen atoms on a surface of palladium (111). The study of the 3D system allowed us to detail the infrared spectrum of H/Pd (111), showing the existence of different adsorption sites on which localized states exist that are strongly coupled (Fermi resonance). This phenomenon governs the diffusion of hydrogen atoms in an ultra-fast time scale (fs).The study of the (6D) H2/Pd(111) system has shown that the transitions observed are in fact transition bands between several quasi-degenerate adsorption states. The agreement between the calculated and measured values is significantly less good than that between the data calculated for the 3D system and the measured data. Does adsorbed hydrogen on palladium exist in the form of a weakly bound H2 molecule? This thesis has provided some answers to this question, which remains open, hovewer, to some extent.

Frontend and backend wearout mechanisms are major reliability concerns for modern microprocessors. In this research, a framework which contains modules for negative bias temperature instability (NBTI), positive bias temperature instability (PBTI), hot carrier injection (HCI), gate-oxide breakdown (GOBD), backend time-dependent dielectric breakdown (BTDDB), electromigration (EM), and stress-induced voiding (SIV) is proposed to analyze the impact of each wearout mechanism on state-of-art microprocessors and to accurately estimate microprocessor lifetimes due to each wearout mechanism. Taking into account the detailed thermal profiles, electrical stress profiles and a variety of use scenarios, composed of a fraction of time in operation, a fraction of time in standby, and a fraction of time when the system is off, this work provides insight into lifetime-limiting wearout mechanisms, along with the reliability-critical microprocessor functional units for a system. This enables circuit designers to know if their designs will achieve an adequate lifetime and further make any updates in the designs to enhance reliability prior to committing the designs to manufacture.

Non-stationary signals, that is signals with time-varying (TV) statistical properties, are commonly encountered in engineering practice. The vibration responses of structures, such as traffic-excited bridges, robotic devices, rotating machinery, and so on, constitute typical examples of non-stationary signals. Structures characterized by properties that vary with time are generally referred as TV structures and their vibration-based identification under normal operating conditions is a significant and challenging problem. An important class of parametric methods for the solution of this problem is based on Functional Series Time-dependent AutoRegressive Moving Average (FS-TARMA) models. These models have parameters that explicitly depend on time, with the dependence described by deterministic functions belonging to specific functional sub-spaces. The focus of the present thesis is on the development of complete and advanced FS-TARMA methods that will offer important improvements in overcoming drawbacks of existent methods and will further foster practical use and application of FS-TARMA models in non-stationary vibration analysis. The specific objectives of the thesis are: a) The introduction of a novel class of Adaptable FS-TARMA (AFS-TARMA) models and the development of a method for their effective identification. AFS-TARMA models are adaptable in the sense that they are not based on basis functions of a fixed form, but instead, they use basis functions with a-priori unknown properties that may adapt to the specific random signal characteristics. b) The postulation of a vector FS-TARMA method for output-only structural identification and the development of effective tools for both model parameter estimation and model structure selection. c) The introduction of a statistical method for vibration-based fault diagnosis in TV structures. d) The presentation of a thorough review on FS-TARMA models covering both theoretical and practical aspects of the model parameter estimation and structure selection problems with special emphasis being placed on promising recent methods. The methods that are developed in each chapter of this thesis are validated through their application in both numerical and experimental case studies and comparisons with currently available non-stationary signal identification methods. The results of the study demonstrate the new methods' applicability, effectiveness, and high potential for parsimonious and accurate identification and dynamic analysis of TV structures. / Μη-στάσιμα σήματα, δηλαδή σήματα με χρονικά μεταβαλλόμενες (ΧΜ) στατιστικές ιδιότητες, απαντώνται συχνά στην επιστήμη του μηχανικού. Τυπικά παραδείγματα αποτελούν οι ταλαντωτικές αποκρίσεις κατασκευών, όπως γέφυρες με κινούμενα οχήματα, ρομποτικές διατάξεις, περιστρεφόμενες μηχανές και άλλες. Κατασκευές που χαρακτηρίζονται από ιδιότητες οι οποίες μεταβάλλονται με τον χρόνο αναφέρονται ως ΧΜ κατασκευές και η δυναμική αναγνώριση και ανάλυση τους επί τη βάση ταλαντωτικών σημάτων απόκρισης αποτελεί σημαντικό και ταυτόχρονα δύσκολο πρόβλημα. Μια σημαντική τάξη παραμετρικών μεθόδων για την επίλυση αυτού του προβλήματος βασίζεται στα συναρτησιακά χρονικά μεταβαλλόμενα μοντέλα αυτοπαλινδρόμησης κινητού μέσου όρου (FS-TARMA, Functional Series Time-Dependent Auto-Regressive Moving Average). Τα μοντέλα αυτά χαρακτηρίζονται απο ΧΜ παραμέτρους οι οποίες ακολουθούν καθοριστικό πρότυπο και κατά συνέπεια μπορούν να προβληθούν σε κατάλληλα επιλεγμένους συναρτησιακούς υποχώρους. Ως βασικός στόχος της παρούσας διατριβής ορίζεται η ανάπτυξη εξελιγμένων μεθόδων μοντελοποίησης FS-TARMA οι οποίες θα προσφέρουν σημαντικές βελτιώσεις στις υπάρχουσες προσεγγίσεις και θα βοηθήσουν στην αντιμετώπιση πρακτικών προβλημάτων που σχετίζονται τόσο με την αναγνώριση των δυναμικών χαρακτηριστικών όσο και την διάγνωση βλαβών σε ΧΜ κατασκευές. Οι συγκεκριμένοι στόχοι της διατριβής μπορούν να περιγραφούν ως ακολούθως: α) Εισαγωγή καινοτόμων προσαρμόσιμων μοντέλων FS-TARMA και ανάπτυξη κατάλληλης μεθόδου για την αποτελεσματική εκτίμηση τους. Τα νέα μοντέλα είναι προσαρμόσιμα υπό την έννοια ότι δεν βασίζονται σε προκαθορισμένες συναρτήσεις βάσης, αλλά αντιθέτως χρησιμοποιούν συναρτήσεις βάσης με εκ των προτέρων άγνωστες ιδιότητες οι οποίες μπορούν να προσαρμοστούν στα χαρακτηριστικά συγκεκριμένου σήματος. β) Ανάπτυξη διανυσματικής μεθόδου εκτίμησης μοντέλων FS-TARMA για την αναγνώριση κατασκευών μέσα από διανυσματικά σήματα ταλαντωτικής απόκρισης. Ανάπτυξη αποδοτικών εργαλείων τόσο για το πρόβλημα εκτίμησης των παραμέτρων όσο και της επιλογής της δομής του μοντέλου. γ) Εισαγωγή στατιστικής μεθόδου για την διάγνωση βλαβών σε ΧΜ κατασκευές μέσω μοντέλων FS-TAR. δ) Παρουσίαση μιας διεξοδικής επισκόπησης των μοντέλων FS-TARMA η οποία καλύπτει τόσο θεωρητικά όσο και πρακτικά ζητήματα των προβλημάτων εκτίμησης των παραμέτρων και επιλογής της δομής των μοντέλων. Η αποτελεσματικότητα των μοντέλων και των μεθόδων που αναπτύσσονται σε κάθε κεφάλαιο αυτής της διατριβής διερευνάται µέσω της εφαρµογής τους τόσο σε αριθµητικές όσο και πειραµατικές µελέτες και συγκρίσεις µε υπάρχουσες µη-στάσιµες µεθόδους αναγνώρισης σηµάτων. Τα αποτελέσματα της εργασίας αυτής επιδεικνύουν την ικανότητα των νέων μοντέλων να παρέχουν εξαιρετικά ακριβείς αναπαραστάσεις ΧΜ κατασκευών κατάλληλων τόσο για την δυναμική ανάλυση όσο και για την διάγνωση βλαβών σε αυτές.

Cette thèse fait partie d’un projet franco-keyan dénommé ELEPHOX (ELEctrochemical and PHOto Properties of Some Remarkable Ruthenium and Iron CompleXes). En particulier, notre focus est la continuation du travail de C. Muhavini Wawire, Damien Jouvenot, Fréd erique Loiseau, Pablo Baudin, Sébastien Liatard, Lydia Njenga, Geoffrey Kamau, et Mark E. Casida, “Density-Functional Study of Lumininescence in Polypyridine Ruthenium Complexes,” J. Photochem. and Photobiol. A 276, 8 (2014). Cet article a proposé une indice orbitalaire de temps de luminescence pour les complexesde ruthénium. Cependant cet article n’était limité qu’à quelques mnolecules. Afin d’avoir une théorie plus fiable et donc potentiellement plus utile, il faudra tester l’indice de luminescence sur beaucoup plus de molécules. Ayant établi le protocol, il était “évident” mais toujours un défi de le tester sur encore une centaine de molécules pour démonter ou infirmer l’indice proposée. Pour ce faire, j’ai examainé les 98 pages de la Table I de A. Juris, V. Balzani, F. Bargelleti, S. Campagna, P. Belser, et A.V. Zelewsky, “Ru(II) polypyridine complexes: Photophysics, photochemistry, electrochemistry, and chemiluminescence,” Chem. Rev. 84, 85 (1988) et j’ai extrait un nombre important de données susceptibles à comparaison avec les résultats des calculs de la théorie de la fonctionelle de la densité (DFT) et la DFT dépendante du temps (TD-DFT). Comme les résultats étaient suffisament encourageant, le modèle DFT était examiné de plus près avec la méthode d’une théorie de champs de ligands (LFT) à la base de la densité des états partielle (PDOS). Ainsi j’ai pu tester l’indice de luminescence proposée précédement par laméthode PDOS-LFT et j’ai trouvé des difficultés avec l’indice initialement proposée. Par contre, nous avons pu proposer une nouvelle indice de luminescence qui, à quelques exceptions près, a une corrélation linéaire avec une barrière énergétique moyenne pour l’état triplet excité dérivée à partir des données experimentales. À l’avenir nous pouvons proposer une investigation plus directe de la barrière sur la surface triplet excité pour remplacer la valeur approximative déduite de l’expérience. Puis nous voulons voir sinotre indice de luminescence s’appliquent aux cas des complexes d’iridium. / This thesis is part of the Franco-Kenyan project ELEPHOX (ELEctrochemicaland PHOto Properties of Some Remarkable Ruthenium and Iron CompleXes)project. In particular, it focused on the continuation of the work ofC. Muhavini Wawire, Damien Jouvenot, Fréd erique Loiseau, Pablo Baudin,Sébastien Liatard, Lydia Njenga, Geoffrey Kamau, and Mark E. Casida,“Density-Functional Study of Lumininescence in Polypyridine RutheniumComplexes,” J. Photochem. and Photobiol. A 276, 8 (2014). That paperproposed a luminescence index for estimating whether a ruthenium complexwill luminesce or not. However that paper only tested the theory ona few molecules. In order for the theory to have a significant impact, itmust be tested on many more molecules. Now that the protocol has beenworked out, it was a straightforward but still quite challenging matter todo another 100 or so molecules to prove or disprove the theory. In order todo so, I went through the 98 pages of Table I of A. Juris, V. Balzani, F.Bargelleti, S. Campagna, P. Belser, and A.V. Zelewsky, “Ru(II) polypyridinecomplexes: Photophysics, photochemistry, electrochemistry, and chemiluminescence,”Chem. Rev. 84, 85 (1988) and extracted data suitable for comparingagainst density-functional theory (DFT) and time-dependent (TD-)DFT.Since the results were sufficiently encouraging, the DFT model was examinedin the light of partial density of states ligand field theory (PDOS-LFT) andthe previously proposed luminescence indices were tested. In fact, the originallyproposed indices were not found to be very reliable but we were able topropose a new luminescence index based upon much more data and in analogywith frontier-molecular orbital ideas. Except for a few compounds, this index provides a luminescence index with a good linear correlation with anexperimentally-derived average excited-state activation energy barrier. Futurework should be aimed at both explicit theoretical calculations of thisbarrier for ruthenium complexes and extension of the luminescence indexidea to iridium complexes.

Ces dernières années, un nouveau type de polymère donneur d’électron pour des applications photovoltaïques a été étudié de manière intensive, les copolymères à faible bande interdite. Ils sont constitués d’un groupement riche en électron (ER) et d’un groupement pauvre (EP) permettant de contrôler les orbitales frontières et d’induire une délocalisation de l’exciton généré lors du processus de photo-excitation. Une large variété de dispositifs est basée sur ces copolymères avec des rendements d’environ 10% et, pour accroitre leur efficacité, il est nécessaire d’avoir une meilleure compréhension de ces polymères pendant le phénomène de photo-absorption. La chimie théorique apparait comme un outil permettant de prédire différentes propriétés optoélectroniques. Au cours de ce travail, nous avons utilisé la théorie de la fonctionnelle de la densité indépendante (DFT) et dépendante du temps (TD DFT) pour simuler les propriétés optiques d’oligomères de taille croissante avec différents groupements ER et EP. Les propriétés optiques des polymères correspondant ont été extrapolées à l’aide du modèle de Kuhn. Ce criblage théorique nous a permis de sélectionner des systèmes prometteurs à base de benzodithiophène, de benzothiadiazole et de benzofurazane qui ont ensuite été synthétisés par couplage de Stille. Les polymères et oligomères obtenus ont été caractérisés par spectroscopie UV-visible et de fluorescence, chromatographie d’exclusion stérique et par RMN dans le but d’observer des relations structure-propriétés et de faire des corrélations entre résultats expérimentaux et théoriques. / During the last decade, a new kind of donor polymers for photovoltaic application have been intensively studied, the low band-gap polymers. They are based on repeating units associating two different moieties, one electron-rich (ER) and one electron-poor (EP), which allow to finely tune the molecular orbitals and to induce a delocalization of the exciton generated upon the photo-excitation process. A large variety of devices are based on such low band-gap polymers, with a power conversion efficiency record around 10%, and, to increase the efficiency, it is necessary to have a better understanding of these polymers during the photo-absorption phenomenon. Computational chemistry isa powerful tool that permits to predict different opto-electronic properties. For this work, we used Density Functional Theory and Time-Dependent Density Functional Theory to compute the optical properties of increasingly large oligomers involving various ER and EP subunits. The optical properties in the polymer limit were then estimated for the different systems by using an extrapolation scheme based on the Kuhn equation. This theoretical screening allowed us to select promising candidates based on benzodithiophene, benzothiadiazole and benzofurazan for syntheses, which were performed by a Stille coupling. The obtained polymers and size-controlled oligomers were further characterized by UV visible spectroscopy, fluorescence, size exclusion chromatography and NMR, in order to extractstructure-properties relationships and correlate experimental results to theoretical data.

The computation of Schrödinger equations in the semiclassical regime presents several enduring challenges due to the presence of the small semiclassical parameter. Standard approaches for solving these equations commence with spatial discretisation followed by exponentiation of the discretised Hamiltonian via exponential splittings. In this thesis we follow an alternative strategy${-}$we develop a new technique, called the symmetric Zassenhaus splitting procedure, which involves directly splitting the exponential of the undiscretised Hamiltonian. This technique allows us to design methods that are highly efficient in the semiclassical regime. Our analysis takes place in the Lie algebra generated by multiplicative operators and polynomials of the differential operator. This Lie algebra is completely characterised by Jordan polynomials in the differential operator, which constitute naturally symmetrised differential operators. Combined with the $\mathbb{Z}_2$-graded structure of this Lie algebra, the symmetry results in skew-Hermiticity of the exponents for Zassenhaus-style splittings, resulting in unitary evolution and numerical stability. The properties of commutator simplification and height reduction in these Lie algebras result in a highly effective form of $\textit{asymptotic splitting:} $exponential splittings where consecutive terms are scaled by increasing powers of the small semiclassical parameter. This leads to high accuracy methods whose costs grow quadratically with higher orders of accuracy. Time-dependent potentials are tackled by developing commutator-free Magnus expansions in our Lie algebra, which are subsequently split using the Zassenhaus algorithm. We present two approaches for developing arbitrarily high-order Magnus--Zassenhaus schemes${-}$one where the integrals are discretised using Gauss--Legendre quadrature at the outset and another where integrals are preserved throughout. These schemes feature high accuracy, allow large time steps, and the quadratic growth of their costs is found to be superior to traditional approaches such as Magnus--Lanczos methods and Yoshida splittings based on traditional Magnus expansions that feature nested commutators of matrices. An analysis of these operatorial splittings and expansions is carried out by characterising the highly oscillatory behaviour of the solution.