Thesis (Ph. D.)--University of Missouri-Columbia, 1997. / Typescript. Vita. Includes bibliographical references (leaves 158-166). Also available on the Internet.

Thesis (Ph. D.)--Texas Christian University, 2009. / Title from dissertation title page (viewed Nov. 2, 2009). Includes abstract. Includes bibliographical references.

Thesis (Ph. D.)--University of Texas at Austin, 2006. / Vita. Includes bibliographical references and index.

Thesis (Ph. D.)--Physics, Georgia Institute of Technology, 2007. / de Heer, Walter A., Committee Chair ; Chou, Meiyin, Committee Member ; Whetten, Robert L., Committee Member ; First, Phillip N., Committee Member ; Pummer, Earl Ward, Committee Member.

This thesis describes the application of coupled-cluster theory to model systems of metallic solids and cold-atom gases. First, I give an overview of both ground- and excited-state coupled cluster theory as background for the main topics in this thesis. Next, I evaluate the accuracy of several cost-saving approaches in estimating the coupled cluster correlation energy for a model metallic system, the uniform electron gas, in the complete basis set and thermodynamic limits. After that, I present calculations of the spectral function of the uniform electron gas in these same limits, the results of which are rationalized by applying a bosonized coupled-cluster theory to an approximate, simplified Hamiltonian that couples plasmons to a structureless core hole state. Finally, I show how coupled-cluster theory captures the many-body nature of two-component Fermi gases with tunable, attractive interactions.

We give an overview of quantum chemical methods with a particular emphasis on the development of high-accuracy quantum chemical models. The reliability of these methods often hinges on whether enough electron correlation is included in the truncated wave function. As an example, we investigate the structures of m-benzyne and its fluorinated derivative, tetrafluoro-m-benzyne where the inclusion of triple excitations is paramount to correctly describe through-bond delocalization of the monocyclic form. At the CCSDT/6-31G** level of theory, the C1–C3 distance of the minimum energy form of m-benzyne is 2.0°A and the profile of the PES along the C1–C3 distance is that of an asymmetric, single-well, in agreement with previous density-functional theory and coupled cluster studies. In addition, the calculated CCSD(T) fundamental frequencies are in excellent agreement with the measured infrared frequencies, thus confirming the monocyclic form of m-benzyne. For tetrafluoro-m-benzyne, however, the increased eclipsing strain between the ring-external Câ X bonds stabilizes the bicyclo[3.1.0]hexatriene form: the C1–C3 distance is calculated at the CCSD(T)/cc-pVTZ level to be approximately 1.75 °A, which is in the range of elongated CC bonds. Computed harmonic vibrational frequencies compare reasonably well with the experimental neon-matrix difference spectrum and provide further evidence for the existence of a bicyclic form. We also report an extension of the coupled cluster iterative-triples model, CC3, to excited states of open-shell molecules, including radicals. We define the method for both spin-unrestricted Hartree-Fock (UHF) and spin-restricted open-shell Hartree-Fock (ROHF) reference determinants and discuss its efficient implementation in the PSI3 program package. The program is streamlined to use at most O(N7) computational steps and avoids storage of the triple-excitation amplitudes for both the ground-and excited-state calculations. The excitation-energy program makes use of a Lowdin projection formalism (comparable to that of earlier implementations) that allows computational reduction of the Davidson algorithm to only the single- and double-excitation space, but limits the calculation to only one excited state at a time. However, a root-following algorithm may be used to compute energies for multiple states of the same symmetry. Benchmark applications of the new methods to the lowest valence 2B1 state of the allyl radical, low-lying states of the CH and CO+ diatomics, and the nitromethyl radical show substantial improvement over ROHF- and UHF-based CCSD excitation energies for states with strong double-excitation character or cases suffering from significant spin contamination. For the allyl radical, CC3 adiabatic excitation energies differ from experiment by less than 0.02 eV, while for the 2§+ state of CH, significant errors of more than 0.4 eV remain. Finally, ground- and excited-state dipole moments are derived diagramatically and were recently developed within the PSI3 quantum chemistry package. However, convergence problems with computing the left-hand excited-state has prevented us from reporting any meaningful results. Thus, future work includes solving this convergence problem before the effects of triple excitations on one-electron properties can be reported with certainty. / Ph. D.

Coupled cluster (CC) and density functional theory (DFT) are highly regarded as robust quantum chemical methods for accurately predicting a wide variety of properties, such as molecular structures, thermochemical data, vibrational spectra, etc., but there has been little focus on the theoretical prediction of optical rotation. This property, also referred to as circular birefringence, is inherent to all chiral molecules and occurs because such samples exhibit different refractive indices for left- and right- circularly polarized light. This thesis focuses on the theoretical prediction of this chiroptic property using CC and DFT quantum chemical models. Several small chiral systems have been studied, including (S)-methyloxirane, (R)-epichlorohydrin, (R)-methylthiirane, and the conformationally flexible molecules, (R)-3-chloro-1-butene and (R)-2-chlorobutane. All predicted results have been compared to recently published gas-phase cavity ringdown polarimetry data. When applicable, well-converged Gibbs free energy differences among confomers were determined using complete-basis-set extrapolations of CC energies in order to obtain Boltzmann-averaged specific rotations. The overall results indicate that the theoretical rotation is highly dependent on the choice of optimized geometry and basis set (diffuse functions are shown to be extremely important), and that there is a large difference between the CC and DFT predicted values, with DFT usually predicting magnitudes that are larger than those of coupled cluster theory. / Ph. D.

Thesis (PhD)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: The study of α clustering is a well-established topic of research in nuclear physics. Recent experimental evidence has revealed the first 2+ excitation of the Hoyle state in 12C, which is known to have a strong α cluster structure. The idea of multi-particle α cluster structures in light nuclear matter has received much attention from theoretical investigations of late. This research has profound implications in the fields of both nuclear structure and nuclear astrophysics. The 20Ne nucleus is a good example for α clustering, since many of its states are known to have α clustering structures. Few low spin states are known at high excitation energies of this nucleus. It is predicted that this nucleus contains a 0+ 5-α cluster state, a so-called ‘Hoyle analogue state’, above its 5-α break-up threshold at Ex = 19.17 MeV. This thesis presents a study of the 20Ne nucleus with the 22Ne(p,t)20Ne reaction at laboratory angles θlab =(0◦, 7◦, 16◦, 27◦). The iThemba LABS K600 magnetic spectrometer was employed with a beam of energy Elab = 60 MeV, incident upon a 22Ne gas target held intact by Aramid foils. The aim was to search for low spin states in 20Ne at excitation energies above Ex = 15 MeV, and, possibly, to find an indication of the 5-α cluster state. Three narrow states were discovered at energies of Ex = 20.59 MeV, Ex = 21.16 MeV and Ex = 21.80 MeV. Calculations performed with the isobaric multiplet mass equation indicate that these states may be T = 2 isobaric analogue states of three known states in 20O. However, shell-model calculations indicate that these states may also have T = 0 or T = 1 isospin values. There is also evidence of a new state at Ex = 17.67 MeV and, possibly, of a collection of new states which could not be resolved at Ex = 18.84 MeV. A tentative candidate for the desired 5-α cluster state was observed, but this will require another measurement with cleaner background to be confirmed. / AFRIKAANSE OPSOMMING: Alfa bondelvorming is ’n gevestigde navorsingsonderwerp in kernfisika. Daar is onlangse bewyse vir die ontdekking van die 2+ opwekking van die Hoyle toestand in 12C, wat ’n erkende alfa bondelstruktuur het. Die idee van multi-alfa bondelstrukture in ligte kerne het onlangs baie aandag geniet in teoretiese ondersoeke. Hierdie navorsing het besondere implikasies vir kernstruktuur, sowel as vir kernastrofisika. Die 20Ne kern bied ‘n ideale voorbeeld vir alfa bondelvorming aangesien dit bekend is dat baie van die kern se toestande alfa bondelstrukture het. Min lae-spin toestande is by ho¨e opwekenergie¨e bekend in hierdie kern. Daar word voorspel dat ’n 0+ 5-alfa bondeltoestand, ’n sogenaamde ‘Hoyle analoogtoestand’, bo die drumpel vir 5-alfa verval by Ex = 19.17 MeV bestaan. Hierdie tesis beskryf ‘n studie van die 20Ne kern met die 22Ne(p,t)20Ne reaksie by laboratorium hoeke van θlab =(0◦, 7◦, 16◦, 27◦). Die K600 magnetiese spektrometer van iThemba LABS is gebruik met ‘n proton bundel, by ‘n energie van Elab = 60 MeV, wat op ‘n 22Ne gas teiken omhul met aramid foelies gerig is. Die doel was om lae-spin toestande in 20Ne by opwekenergie¨e bo Ex = 15 MeV op te spoor, en om moontlik ook ‘n aanduiding van die 5-alfa bondeltoestand te vind. Drie smal toestande is by energie¨e van Ex = 20.59 MeV, Ex = 21.16 MeV en Ex = 21.80 MeV opgespoor. Berekeninge wat met die isobariese multiplet massa vergelyking uitgevoer is, dui daarop dat hierdie toestande T = 2 isobariese analoogtoestande van drie bekende toestande in 20O kan wees, hoewel skilmodel berekeninge ook T = 0 en T = 1 kandidate aandui. Daar is ook bewyse van ’n nuwe toestand by Ex = 17.67 MeV, en moontlik van ’n versameling nuwe toestande rondom Ex = 18.84 MeV wat nie uitmekaar geken kon word nie. ‘n Tentatiewe kandidaat vir die gesogte 5-alfa bondel toestand is waargeneem, maar nog ‘n meting met ’n skoner agtergrond word vir bevestiging benodig.

Vaggeryd is a rural municipality and wants to develop its rural areas. Therefore Vaggeryd’s municipality wants to become a cluster region within the equus industries and hence become an equine municipality where equestrians can live and run their businesses as well as providing for equine activities and competitions. The reason why it is interesting to create a cluster region is because it comes with benefits for the companies and it helps developing the regional economy (Enright, 1998; Porter, 2000). “Clusters lower barriers to new business formation that improve the environment for productivity.” (Porter, 1998a). One investment made in 2005 in the direction of becoming an equine municipality was the start up of an Advanced Vocational Education [KY] in the region, named Horse Entrepreneur. All 23 students in this programme, year 2005 and 2006, were interviewed and it turned out that all of them wanted to start up own businesses within 10 years, but only three planned to establish their companies in Vaggeryd. Most of the students planned to move back to their home municipality. Eight students in total could, however imagine themselves establishing in Vaggeryd. The students thought that this kind of education is very important for equestrians who want to start up businesses. The students believed that Vaggeryd’s municipality will become a good and functional equine municipality and referred to the highway E4 (which runs through the municipality), the race track and the veterinary clinic. More farms with large lands are what the students think the municipality council should invest in to attract equine companies as well as to become an equine friendly municipality. From the cluster analysis a similar result was found. It showed that there is no agglomeration in the four investigated industries over Sweden, namely horse breeding, horse competitions, managing race tracks and gallops courses and riding educational services and horse rents. This means that the places where the entrepreneurs choose to set up their businesses are less important; hence they can likewise set up in Vaggeryd. However a trend was expected. The districts where most of the equine businesses in Sweden take place are rural areas close to populated regions, so called semi-urban areas. There are no cities in Vaggeryd’s municipality only two towns, Vaggeryd and Skillingaryd. The conclusion drawn is that if Vaggeryd wants to become an equine municipality it must invest (Enright, 1998; Malmberg, 2002). For example creating job opportunities, and building farms on areas with large lands. These investments are needed to attract inhabitants and business people to their municipality before the equine companies can flourish. Investments make this type of clusters attractive (Enright, 1998; Malmberg, 2002). The cluster data revealed that there are no equine activities in Vaggeryd’s municipality today; however it has the possibility to become an equine municipality due to suitable condition, for example land plots with lakes and the closeness to highway E4. Vaggeryd should focus on facilitating business activities and providing with updated networks in order for companies to gain from being clustered, according to the cluster theory advocated by von Hippel (1988) and Hakansson (1987). Vaggeryd suits for equine businesses which are trading goods and services with other businesses, hence which are not dependent on a location close to cities, according to Karlsson (2008) in the field of clustering in smaller regions.

Ferroelectric and ferromagnetic alloy clusters are produced and studied in molecular beams. Nb clusters doped with 1-3 impurity atoms are ferroelectric with low transition temperatures. The alloy clusters with an even number of valence electrons have larger dipole moments than those with odd number of valence electrons. The ferroelectricity is suppressed by magnetic impurities or thermal excitations, and is enhanced by Au and Al doping. The observations strongly suggest that electron-pairing interactions exist in Nb clusters, which indicates Cooper pairing in clusters. The magnetic moments of Co clusters doped with small fraction of Mn,V and Al are studied and compared with those of the bulk alloys. CoMn alloy clusters have enhanced average magnetic moments with Mn doping, which is opposite to the behavior of bulk CoMn. CoV and CoAl alloy clusters behave similarly to their bulk counterparts. We explain the experimental results using the virtual-bound-state model. Finally, the magnetic properties of BiMn clusters are studied in molecular beams. The Mn local moments are found to couple ferromagnetically or ferrimagnetically depending on the composition of the clusters.