To follow up on the unexpectedly-good performance of coupled-cluster models with approx- imate inclusion of 3-body clusters [J. Chem. Phys. 151, 064102 (2019)] we performed a more complete assessment of the 3CC method [J. Chem. Phys. 125, 204105 (2006)] for accurate computational thermochemistry in the standard HEAT framework. New spin- integrated implementation of the 3CC method applicable to closed- and open-shell systems utilizes a new automated toolchain for derivation, optimization, and evaluation of operator algebra in many-body electronic structure. We found that with a double-zeta basis set the 3CC correlation energies and their atomization energy contributions are almost always more accurate (with respect to the CCSDTQ reference) than the CCSDT model as well as the standard CCSD(T) model. The mean errors in { 3CC, CCSDT, and CCSD(T) } electronic (per valence electron) and atomization energies were {23, 69, 125} μEh/e and {0.39, 1.92, 2.57} kJ/mol, respectively. The significant and systematic reduction of the error by the 3CC method and its lower cost than CCSDT suggests it as a viable candidate for post-CCSD(T) thermochemistry application. / Doctor of Philosophy / Stepping into the information age, the computing power has rapidly grown over the last half century. Solving chemical problems on computers has improved lives by reducing the cost and time of researching critical technologies. Scientific research is evolving and experimental finding are now supported with a computational model. Doing chemistry on computers requires quantum simulations, which is essentially solving the Schr ̈odinger equation on a computer that simulates a wave function for all the electrons in a system. Different models are built based on how these inter electronic interactions are treated. To predict results with accuracy on par with the experimental findings requires using higher-order wave functions methods.These are computationally expensive and often not practical. The lower-order methods that are easy to implement can be found in all quantum chemistry software packages. On the other hand, the higher-order methods are laborious and error prone to implement manually due to the sheer complexity of theory. Debugging such implementations often requires a lot of effort with the uncertainty in returns. To solve this problem, we implemented a second-quantization toolkit (SeQuant version 2.0) that derives many-body methods, specifically the general-order coupled cluster (CC) model. The CC model is systematically improvable and accurate. One such CC model, the CCSD(T), has been called the gold standard in quantum chemistry. For compactness, these equations are usually derived in their spin-orbital form. The evaluation and storage cost of these methods is reduced up to four-fold by transforming the spin-orbital expressions to a spin-traced form. In this work, the spin-tracing algorithms are described in detail. The general-order coupled cluster approach is used to derive the internally corrected approximate coupled cluster methods. These methods improve the accuracy of a model at a reduced cost. For small molecules, it was observed that the spin-traced evaluation was over three times faster than spin-orbital coupled cluster. To further reduce the cost of calculations, we added explicit correlation to our CC models. These methods improved the quality of our results with a modest increase in the computational cost.

In this dissertation we report on the application of the Liouville Operator Resolvent technique (LRM) to two hamiltonians used to model highly correlated systems: Falicov-Kimball and Anderson Lattice. We calculate specific heats, magnetic susceptibilities, thermal averages of physical operators, and energy bands. We demonstrate that the LRM is a viable method for investigating many body problems. For the Falicov-Kimball, an exact calculation of the atomic limit shows no sharp metal-insulator transition. A truncation approximation for the full hamiltonian has a smooth evolution from the atomic limit with the opening of a band for the conduction electrons. No phase transition was observed. A bose space calculation using the proper boson norm indicates that the conduction band induces a correlation between localized electrons on nearest-neighbor sites. It is not known if this effect is real or a by-product of the approximation. We applied the LRM to the Anderson Lattice and several of its limiting cases. In the limit of no hybridization, for both the symmetric and asymmetric (mixed-valence) parameter sets, we found that the thermodynamics could be described as competition between closely-lying energy levels. The effects that dominate are those that minimize the thermal average of the hamiltonian. A simple model is presented in which only hybridization between two localized orbitals is allowed. It shows that hybridization can give rise to mixed valence phenomena as the temperature approaches zero. For the full Anderson Lattice hybridization causes relatively small shifts in the occupation numbers of the localized and conduction electrons. However, these shifts can have dramatic effects on the physical properties as demonstrated by the magnetic susceptibilities. Band structures of the eigenenergies of the Liouville operator, for both parameter sets, reveal that low-lying excitations associated with some of the basis vector operators may split out from the fermi level and become significant at low temperatures. In addition, we report on progress toward extending the calculation to bose space using a commutator norm. / Ph. D. / incomplete_metadata

We study elastic and inelastic (2 cluster) - (2 cluster) scattering amplitudes for N-body quantum systems. For potentials falling off like r⁻^-1-E we prove that below the lowest 3-cluster threshold these amplitudes exist, are continuous and that asymptotic completeness holds. Moreover, if potentials fall off exponentially we prove that these amplitudes can be meromorphically continued in the energy, with square root branch points at the 2 cluster thresholds. / Ph. D.

This doctoral thesis presents an extensive study on the applications of generalized coherent states (GCS) for the quantum dynamics of many-body systems. The research starts with exploring the fundamental properties of generalized coherent states, which are created by generators of the SU($M$) group acting on an extreme state, and demonstrating their role in representing ideal quantum condensates. A significant feature is the relationship between generalized coherent states and the more standard Glauber coherent states (CS). Similarities in their overcomplete and non-orthogonal nature are shown, alongside crucial differences with respect to $U(1)$ symmetry and entanglement properties, which generalized coherent states solely adhere to. Furthermore, this thesis delves into the nonequilibrium dynamics of GCS as well as Glauber CS under nonlinear interactions. Combining analytical analysis and numerical calculations, it is found that while their two-point correlation functions are equivalent in the thermodynamic limit, their autocorrelation functions exhibit distinctly different characteristics. It is proven analytically that the autocorrelation functions of the evolved GCS relate to the ones of the corresponding Glauber CS through a Fourier series relation, which arises due to the $U(1)$ symmetry of the GCS. A substantial part of this thesis is dedicated to investigating the dynamics of the Bose-Hubbard model, incorporating both nonlinear interaction and tunneling term. This investigation introduces a novel approach which employs an Ansatz for the wave function in terms of a linear combination of GCS, where the differential equations of all the variables are determined by the time-dependent variational principle without truncation. This innovative method is adeptly applied to the nonequilibrium dynamics in various scenarios, from the bosonic Josephson Junction model where some fundamental quantum effects can be revealed by a handful of GCS basis functions, to large system size implementations of the Bose-Hubbard model, where the phenomenon of thermalization can be observed. The proposed variational approach provides an alternative way to study the time-dependent dynamics in many-body quantum systems conserving particle number. The final focus of this thesis is on the boson sampling problem within a linear optical network framework. Again adapting a linear combination of GCS, an exact analytical formula for the output state in standard boson sampling scenarios is derived by means of Kan's formula, showcasing a computational complexity that increases less severely with particle and mode number than the super-exponential scaling of the Fock state Hilbert space. The reduced density matrix of the output state is obtained by tracing out one subsystem. This part of the study extends to examining the properties of the subsystem entanglement creation, and offering novel perspectives on entanglement entropy differences between global and local optical networks. This thesis makes several contributions to the field of quantum many-body systems, particularly highlighting the potential applications of GCS. The presented research offers a new variational method to the nonequilibrium dynamics, and paves the way for future explorations and applications in quantum simulations, quantum computing and beyond.

Many-Body Perturbation Theory is put to test as a method for reliable calculations of the electron-electron interaction in two-dimensional quantum dots. We show that second order correlation gives qualitative agreement with experiments on a level which was not found within the Hartree-Fock description. For weaker confinements, the second order correction is shown to be insufficient and higher order contributions must be taken into account. We demonstrate that all order Many-Body Perturbation Theory in the form of the Coupled Cluster Singles and Doubles method yields very reliable results for confinements close to those estimated from experimental data. The possibility to use very large basis sets is shown to be a major advantage compared to Full Configuration Interaction approaches, especially for more than five confined electrons. Also, the possibility to utilize two-electron correlation in combination with tailor made potentials to achieve useful properties is explored. In the case of a two-dimensional quantum dot molecule we vary the interdot distance, and in the case of a two-dimensional quantum ring we vary the ring radius, in order to alter the spectra. In the latter case we demonstrate that correlation in combination with electromagnetic pulses can be used for the realization of quantum logical gates. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 5: Manuscript.

Thesis (MSc (Physics))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: Non-commutative quantum mechanics is a generalisation of quantum mechanics which incorporates the notion of a fundamental shortest length scale by introducing non-commuting position coordinates. Various theories of quantum gravity indicate the existence of such a shortest length scale in nature. It has furthermore been realised that certain condensed matter systems allow effective descriptions in terms of non-commuting coordinates. As a result, non-commutative quantum mechanics has received increasing attention recently. A consistent formulation and interpretation of non-commutative quantum mechanics, which unambiguously defines position measurement within the existing framework of quantum mechanics, was recently presented by Scholtz et al. This thesis builds on the latter formalism, extends it to many-particle systems and links it up with non-commutative quantum field theory via second quantisation. It is shown that interactions of particles, among themselves and with external potentials, are altered as a result of the fuzziness induced by non-commutativity. For potential scattering, generic increases are found for the differential and total scattering cross sections. Furthermore, the recovery of a scattering potential from scattering data is shown to involve a suppression of high energy contributions, disallowing divergent interaction forces. Likewise, the effective statistical interaction among fermions and bosons is modified, leading to an apparent violation of Pauli’s exclusion principle and foretelling implications for thermodynamics at high densities. / AFRIKAANSE OPSOMMING: Nie-kommutatiewe kwantummeganika is ’n veralgemening van kwantummeganika wat die idee van ’n fundamentele kortste lengteskaal invoer d.m.v. nie-kommuterende ko¨ordinate. Verskeie teorie¨e van kwantum-grawitasie dui op die bestaan van so ’n kortste lengteskaal in die natuur. Dit is verder uitgewys dat sekere gekondenseerde materie sisteme effektiewe beskrywings in terme van nie-kommuterende koordinate toelaat. Gevolglik het die veld van nie-kommutatiewe kwantummeganika onlangs toenemende aandag geniet. ’n Konsistente formulering en interpretasie van nie-kommutatiewe kwantummeganika, wat posisiemetings eenduidig binne bestaande kwantummeganika raamwerke defineer, is onlangs voorgestel deur Scholtz et al. Hierdie tesis brei uit op hierdie formalisme, veralgemeen dit tot veeldeeltjiesisteme en koppel dit aan nie-kommutatiewe kwantumveldeteorie d.m.v. tweede kwantisering. Daar word gewys dat interaksies tussen deeltjies en met eksterne potensiale verander word as gevolg van nie-kommutatiwiteit. Vir potensiale verstrooi ¨ıng verskyn generiese toenames vir die differensi¨ele and totale verstroi¨ıngskanvlak. Verder word gewys dat die herkonstruksie van ’n verstrooi¨ıngspotensiaal vanaf verstrooi¨ıngsdata ’n onderdrukking van ho¨e-energiebydrae behels, wat divergente interaksiekragte verbied. Soortgelyk word die effektiewe statistiese interaksie tussen fermione en bosone verander, wat ly tot ’n skynbare verbreking van Pauli se uitsluitingsbeginsel en dui op verdere gevolge vir termodinamika by ho¨e digthede.

The repulsive delta-function interaction model in one dimension is reviewed for spinless particles and for spin-1/2 fermions. The problem of solving the differential equation related to the Schrödinger equation is reduced by the Bethe ansatz to a system of algebraic equations. The delta-function interaction is shown to have no effect on spinless fermions which therefore behave like free fermions, in agreement with Pauli's exclusion principle. The ground-state problem of spinless bosons is reduced to an inhomogeneous Fredholm equation of the second kind. In the limit of impenetrable interactions, the spinless bosons are shown to have the energy spectrum of free fermions. The model for spin-1/2 fermions is reduced by the Bethe ansatz to an eigenvalue problem of matrices of the same sizes as the irreducible representations R of the permutation group of N elements. For some R's this eigenvalue problem itself is solved by a generalized Bethe ansatz. The ground-state problem of spin-1/2 fermions is reduced to a generalized Fredholm equation.

Diese Dissertation beschäftigt sich mit theoretischen Untersuchung der elektronischen und magnetischen Eigenschaften von 4f-Systemen mit Filmgeometrie. Die vorgestellte Theorie basiert auf dem s-f-Modell, welches durch einen intra-atomaren Austausch zwischen einem System lokaler magnetischer Momente und den Leitungselektronen charakterisiert ist. Das Modell wird für den Fall des leeren Leitungsbandes untersucht. Der untersuchte Spezialfall ist anwendbar auf die Klasse der ferromagnetischen Halbleiter mit den Europiumchalkogeniden EuO und EuS als Prototypen solcher Substanzen. Für den Grenzfall ferromagnetischer Sättigung des Systems lokaler magnetischer Momente existiert eine exakte Lösung für das Problem. Für endliche Temperaturen wird eine Methode vorgestellt, die auf einer momentenerhaltenden Entkopplungsprozedur für passend definierte Green-Funktionen basiert. Die Theorie für endliche Temperaturen leitet sich dabei übergangslos aus dem exakt lösbaren Grenzfall ab. Mit Hilfe der vorgestellten Theorie wird das temperaturabhängige Quasiteilchenspektrum eines ferromagnetischen Modellfilmes berechnet. Die Rechnungen zeigen ein deutliches korrelationsinduziertes Aufspalten der Spektren, das in der Existenz eines neuen Quasiteilchens, des magnetischen Polarons, resultiert. Der zweite Teil der Dissertation beschäftigt sich mit der Berechnung der elektronischen und magnetischen Eigenschaften eines realen ferromagnetischen Halbleiterfilms. Um den vielfachen Leitungsbändern eines realen Systems Rechnung tragen zu können, wird das ursprüngliche s-f-Modell zu einem Mehrbandmodell erweitert. Das so erweiterte s-f-Modell wird dazu benutzt, die temperaturabhängige Bandstruktur von Volumen-EuO und von EuO(100)-Filmen zu berechnen. Die T=0-Bandstrukturen, die als Input für die Modellrechnungen dienen, werden hierbei mittels einer TB-LMTO-ASA-Bandstrukturrechnung berechnet. Die spezielle Struktur der Lösung des s-f-Modells für den exakt lösbaren Grenzfall von T=0 verhindert dabei das Auftreten von Doppelzählungen relevanter Wechselwirkungen bei der Kombination von ab-initio-Rechnungen und s-f-Modellrechnungen. Die erhaltenen temperaturabhängigen Bandstrukturen geben wertvolle Einblicke in das Wechselspiel zwischen elektronischen und magnetischen Eigenschaften in EuO-Systemen und gestatten es, verifizierbare Vorhersagen für künftige Experimente zu machen. Insbesondere wird die Existenz eines EuO(100)-Oberflächenzustandes vorhergesagt, der das Auftreten eines Oberflächen-Metall-Isolator-Übergangs induzieren kann. / This dissertation is concerned with the theoretical investigation of the electronic and magnetic properties of 4f systems with film geometry. The presented theory is based on the s-f model which features an intra-atomic exchange between a system of localized magnetic moments and the conduction electrons. The model is investigated for the special case of zero band occupation of the conduction bands which is applicable to the situation in ferromagnetic semiconductors such as the europium chalcogenides EuO and EuS. For the special case of ferromagnetic saturation of the local-moment system the problem is exactly solvable. For finite temperatures, the presented approach is based on a moment-conserving decoupling approximation for suitably defined Green functions and evolves continuously from the exact limiting case. The theory is used to calculate the temperature-dependent quasiparticle spectrum of a ferromagnetic model film. Within these calculations, one finds a marked correlation-induced splitting of the spectra resulting in the existence of a new quasiparticle, the magnetic polaron. The second part of the thesis is devoted to the calculation of the electronic and magnetic properties of a real ferromagnetic semiconductor film. The original s-f model is extended to a multi-band s-f model to account for the multiple conduction bands in a real system. Based on the resulting model, the temperature-dependent band structures of bulk EuO and EuO(100) films are calculated. Here, the T=0 band structures of the systems, which have to be taken as input for the model calculations, are calculated using the TB-LMTO-ASA band-structure technique. Due to the special form of the solution of the s-f model for the exactly solvable limiting case of T=0 the employed approach for combining the first-principles calculations with the model calculations prevents the problem of double counting of relevant interactions. The calculated temperature-dependent band structures yield a valuable insight into the temperature-dependent interplay between the magnetic and electronic properties in the EuO systems and allow to make verifiable predictions for future experiments. In particular, the existence of a EuO(100) surface state has been predicted and been shown to possibly induce a surface insulator-metal transition.

No description available.

Many-body perturbation theory and coupled-cluster theory, combined with carefully constructed basis sets, can be used to accurately compute the properties of small molecules. We applied a series of methods and basis sets aimed at reaching the ab initio limit to determine the barrier to planarity for ethylene cation. For potential energy surfaces corresponding to bond dissociation, a single Slater determinant is no longer an appropriate reference, and the single-reference hierarchy breaks down. We computed full configuration interaction benchmark data for calibrating new and existing quantum chemical methods for the accurate description of potential energy surfaces. We used the data to calibrate single-reference configuration interaction, perturbation theory, and coupled-cluster theory and multi-reference configuration interaction and perturbation theory, using various types of molecular orbitals, for breaking single and multiple bonds on ground-state and excited-state surfaces. We developed a determinant-based method which generalizes the formulation of many-body wave functions and energy expectation values. We used the method to calibrate single-reference and multi-reference configuration interaction and coupled-cluster theories, using different types of molecular orbitals, for the symmetric dissociation of water. We extended the determinant-based method to work with general configuration lists, enabling us to study, for the first time, arbitrarily truncated coupled-cluster wave functions. We used this new capability to study the importance of configurations in configuration interaction and coupled-cluster wave functions at different regions of a potential energy surface.