The work presented in this thesis is dedicated to developing inexpensive quantum-chemical models that are able to produce smooth and physically correct potential energy curves for the dissociation of single covalent bonds. It is well known that the energies produced by many ab initio theories scaling as the fifth order with the system size (for instance, second-order Moller-Plesset (MP2) and Epstein-Nesbet perturbation theories) diverge at large interatomic separations. We show that the divergent behavior of such perturbation schemes is due to a small number of terms in the energy expressions. Then, we demonstrate that the self-consistent replacement of these terms by their analogs from the coupled cluster theory (such as CCSD) allows one to redress the erroneous behavior of the perturbation theories without the damage to the overall scaling. We also investigate the accuracy of these hybrid perturbation theory-coupled cluster theories near equilibrium geometry. Judging from the computed spectroscopic constants and shapes of the potential energy curves, one such model, denoted MP2-CCSD(II) in this work, performs consistently better than the MP2 theory at essentially the same computational cost.

Accurate energetic modeling of large molecular systems is always desired by chemists. For example, ligand-protein binding simulations and enzymatic catalysis studies all involve with a small energy difference. The energetic accuracy depends largely on a proper handling of electronic correlations. Molecular mechanics (MM) methods deliver a parameterized Newtonian treatment to these problems. They show great capability in handling large calculations but give only qualitatively good results. Quantum mechanics (QM) methods solve Schrödinger equations and exhibit much better energy accuracy, though the computational cost can be prohibitive if directly applied to very large systems. Fragment-based methods have been developed to decompose large QM calculations into fragment calculations. However, most current schemes use a self- consistent field (SCF) method on fragments, in which no electronic correlation is accounted for. The super-system energy is computed as a sum of fragment energies plus two-body corrections and, possibly, three-body corrections (a "body" is a fragment). Higher order corrections can be added. Nevertheless, many problems require the treatment of high order electronic correlations. The coupled-cluster (CC) theory is the state-of-the-art QM method for handling electronic correlations. The CC wavefunction contains correlated excitations up to a given truncated level and coincidental excitations for all possible electronic excitations. It is a brilliant way of including more electronic correlations while maintaining a low-order scaling. In the proposed excitonic coupled-cluster (X-CC) theory, substantial modifications have been made to allow CC algorithms to act on the collective coordinates of fragment fluctuations to obtain super-system energy. The X-CC theory is designed to achieve accurate energetic modeling results for large chemical systems with much improved affordability and systematic improvability. The test system used in this work is a chain of beryllium atoms. A 30-fragment X-CCSD(2) calculation delivered matching accuracy with traditional CCSD method. An X-CCSD(2) calculation on a chain of 100 bonded fragments finished in 7 hours on a single 2.2 GHz CPU core. The X-CC scheme also demonstrates the ability in handling charge transfer problems. Due to the use of fluctuation basis in the test cases, the excitonic algorithms can be easily generalized to inhomogeneous systems. This will be investigated in future work.

The thesis focuses on Denis Dutton's cluster definition of art, its critique and possible defence in the context of evolutionary aesthetics. The main theme that accompanies the thesis is the connection between the evolutionary origins of art and its definition today. After an introductory presentation of evolutionary aesthetics' approaches to the search for the origin and definition of art, the central section is devoted to Dutton's cluster theory. This is presented from two perspectives - against the background of his understanding of the Darwinian-inspired concept of art, that is, based on natural and sexual selection, and against the background of Berys Gaut's original cluster theory. Dutton's theory has faced criticisms of the normative universalism that his evolutionary theory has the potential to set up, the subjectivity regarding antipathy to modern art, and the over-openness of the cluster. The thesis will attempt to evaluate the critique and to clarify whether Dutton succeeds in advocating a link between the origins of art and its modern definition. Keywords: Denis Dutton, evolutionary aesthetics, darwinism, adaptation, cluster theory, definition of art.

Studiens syfte är att undersöka om bolag på Öresunds kommersiella fastighetsmarknad efterföljer sina avsedda strategier. Wihlborgs, Vasakronan och Klövern har valts ut för studien då de tillsammans innehar betydande marknadsandelar över Öresunds kommersiella fastighetsmarknad. Bolagen har undersökts för att utläsa om de påverkats av dagliga processer samt om de efterföljer varandras beteende, så kallat hordbeteende. Studien har genomförts med en kvalitativ metod för att kunna observera förändringar i strategier och dess genomförande på djupet. Bolagens strategier för ägande, förvärv och avyttring har studerats. Därtill har en djupgående granskning av samtliga bolags fastighetstransaktioner fullföljts. Detta för att bilda en uppfattning om var bolagen har förvärvat och avyttrat i praktiken. Den samlade information har hämtats från årsredovisningar, pressmeddelanden och tidningsartiklar.Bolagens strategier och informationen om var de har förvärvat samt avyttrat har kompletterats med kvalitativa intervjuer med transaktions- och investeringsansvariga på respektive bolag. Den teoretiska referensramen kännetecknas av strategisk teori och klusterteori med ett övergripande stöd av finansiell beteendevetenskap. Med stöd av teorin har studiens frågeställning prövats och utrett om bolagen efterföljer sin avsedda strategi och eventuella motiv bakom detta. Bolagen påverkas inte i någon större grad av mikroprocesser och instinkter. Wihlborgs, Klövern och Vasakronan efterföljer i mångt och mycket sina avsedda strategier. En majoritet av förvärven sker på valda delmarknader. Fördelarna som bolagen ser på deras valda delmarknader beskrivs som effektivare förvaltning, uthyrning, koordinering av hyresgäster samt en ökad attraktivitet för kund. Bolagen har under den studerade tidsperioden endast investerat på de valda delmarknaderna men avyttrat en del strategiska fastigheter. Två av respondenterna påpekar att strategiskt passande fastigheter kan avyttras om marknaden bjuder högre än vad bolagen har värderat fastigheten till. Det finns dock svårigheter att dra slutsatser för om aktörerna imiterar varandra eller inte. Detta då mycket information hålls internt. / The purpose of this study is to examine whether companies on the Oresund commercial real estate market stay true to their intended strategies. Wihlborgs, Vasakronan and Klövern have been selected for the study as they together have a considerable amount of market shares in the Oresund commercial real estate market. The study emphasis on whether daily processes affect the companies and whether they mimic each other, so called horde behavior. The study has been carried out with a qualitative method in order to observe any changes in the companies’ strategies and activities in depth. The companies’ strategies for their ownership, acquisition and disposal of properties have been studied. In addition has an in depth examination of the companies real estate transactions been made. This, in order to form an estimation on where the companies in practice have acquired and disposed properties. The information has been retrieved from annual financial reports, press releases and news articles.The strategies and the information regarding the transactions have been supplemented with qualitative interviews with transaction- and investment managers from the three companies. The theoretical framework is characterized by strategic theory and cluster theory with an overall support from behavioral finance. The question at issue is tested towards the theoretical areas and whether the companies follow their intended strategy and possible motives behind this. The companies are not affected to a great extent by micro processes and instincts. Wihlborgs, Klövern and Vasakronan follow their plans in numerous ways. A majority of the acquisitions take place in selected submarkets. The benefits of the selected submarkets are described as more efficient management, rental, coordination of tenants and an increased customer attractiveness. During the studied period, the companies only invested in the selected submarkets, but disposed of some strategic properties. Two of the respondents respondents point out that strategically sutiable real estate can be disposed of if the market bids higher than the companies have valued the property. There are however difficulties regarding the conclusion if the companies mimic each other. This is due to much of the information is kept internally.

This thesis is based on a detailed analysis of various topics related to the question of whether video games can be art. In the first place it analyzes the current academic discussion on this subject and confronts different opinions of both supporters and objectors of the idea, that video games can be a full-fledged art form. The second point of this paper is to analyze the properties, that are inherent to video games, in order to find the reason, why cultural elite considers video games as inferior in relation to traditional forms of art. In addition to features of games like entertainment, competitivness and unproductivity, this part examines the circumstances that have an impact on current game design, like mass popularity and game developers pandering to wide audiance. Due to these circumstances, the majority of video games can be considered kitsch. Following passage through the application of theory of kitsch on specific video game shows and identifies tendencies in game design that cause this condition. Conclusion of the second chapter, however, shows that some video games exhibit characteristics that are generally regarded as positive elements of art works and by that they avoid being branded as kitsch. The last part of this thesis, based on cluster theory of art, identifies and analyzes...

L'importance des effets relativistes dans la chimie a été reconnu depuis les années 1980. Par exemple, sans la relativité (a) l'or aurait la même couleur que l'argent (b) le mercure ne serait pas liquide à la température ambiante et (c) nos voitures ne démarrent pas avec une batterie de plomb. Pour une description théorique de la structure et la réactivité des éléments lourds, la relativité est un ingrédient essentiel. Le hamiltonien pour les calculs moléculaires relativistes à 4 composantes est construit en remplaçant la partie mono-électronique de l'hamiltonien électronique non-relativiste par le hamiltonien de Dirac. La partie bi-électronique est approchée par le terme de r Coulomb comme dans le cas non relativiste, ce qui donnel'hamiltonien de Dirac-Coulomb (DC). Pour réduire le coût de calcul, on peut utiliser des hamiltoniens relativistes à 2 composantes. Parmi eux, l'hamiltonien exact à 2 composantes (X2C) est le plus précise. La corrélation électronique est, cependant, une contribution très importante pour obtenir une description théorique à la fois qualitative et quantitative des spectroscopies moléculaires, réactions, etc. Dans cette thèse, nous avons étudié l'interaction entre la relativité et de la corrélation. à la fois par des développements méthodologiques et par des applications moléculaires. Dans la première partie de la thèse, nous avons calculé les constantes spectroscopiques dimères des gaz rares lourds. La liaison faible de ces dimères ne peut être décrit que par l'inclusion de la corrélation électronique. Les dimères des gaz rares les plus lourds, le radon et l'eka-radon, nécessite de plus un traitement adéquat de la relativité. Nos calculs sont basés sur l'hamiltonien X2Cmmf, à la fois avec des méthodes de corrélation basés sur une fonction d'onde et séparation de porte (srDFT). La deuxième partie de cette thèse concerne la simulation de la spectroscopie des rayons X, où l'on sonde la région du cœur d'une molécule, ou la relativité joue un rôle très important. Nous avons étudié la spectroscopie L-edge de la série isoélectronique: UO22 +, UNO+, et UN2, où le couplage spin-orbite joue un rôle majeur. Au niveau des méthodes, nous avons considéré MP2 à couches ouvertes et la théorie de la fonctionnelle de la densité dépendante de temps (TDDFT). Dans un autre étude, nous avons simulé la spectroscopie K-edge de la série H2X (X = O, S, Se, Te) et XH3 (X = N, P, As) ainsi que les molécules N2 et N2O2. Pour ces systèmes, l'interaction spin-orbite est moins important. Par conséquent, nous avons utilisé un hamiltonien DC sans spin (SF). Certains des systèmes pris en compte dans ce travail sont de caractère multi-référentielles ; nous avons utilisé la methode Coupled Cluster Multi-référentielle de type State Universal et adapté au groupe unitaire (UGA-SUMRCC) comme une méthode de corrélation. Dans la troisième et partie principale de la thèse, l'attention est de nouveau sur la relativité et de la corrélation, mais pour le calcul des propriétés électriques et magnétiques moléculaires. Nous avons développé et mis en œuvre un module pour le calcul des valeurs moyennes au niveau relativiste à 4-composantes coupled cluster monoréferentiel. Les propriétés qui sondent la densité électronique près de noyaux (lourds), telles que la résonance paramagnétique électronique (RPE), les paramètres des gradients de champ électrique et la non-conservation de la parité (NCP) des molécules chirales ,sont parfaitement adaptés pour l'application de cette méthode. Pour l'instant, nous avons étudié que la NCP. Ce module dans le logiciel DIRAC pour les calculs moléculaires relativistes fournit un cadre propice pour la mise en œuvre de méthodes de CC relativistes employant la symétrie de groupes doubles et de permutation de manière très efficace. En perspective, nous ciblons la mise en œuvre de la réponse linéaire CC pour le calcul des énergies d'excitation et propriétés moléculaires de second ordre tels que les paramètres de RMN. / The importance of relativistic effects in chemistry has been recognized since the 1980s. Without relativity (a) gold would have the same colour as silver (b) mercury would not be liquid at room temperature (c) our cars would not start (lead-battery). For a theoretical description of the structure and reactivity of heavy-elements, relativity is considered as an essential ingredient. The Hamiltonian for the 4-component relativistic molecular calculations is constructed by replacing the one-electronic part of the non-relativistic molecular Hamiltonian by the Dirac Hamiltonian. The two-electronic part of the Hamiltonian is approximated by the Coulombic repulsion term as in the non-relativistic case. The resulting Hamiltonian is called the Dirac-Coulomb (DC) Hamiltonian. For chemical applications there exist a class of relativistic Hamiltonians, where one-electronic part of the DC Hamiltonian is transformed to a 2-component one. Among them the eXcact 2-component (X2C) Hamiltonian is the most accurate one. Electron correlation, however, is a very important contribution to achieve a both qualitative and quantitative correct description of molecular spectroscopies, reactions etc. It is, therefore, essential to study the interplay between relativity and correlation. In this thesis, we have studied this interplay both in terms methodological developments and molecular applications. In the first part of the thesis we have studied the spectroscopic constants of the heavy rare gas dimers. The weak bonding of those dimers can only be described by the inclusion of electron correlation. The heavier analogues in the rare gas series i.e, Radon and eka-Radon, in addition require adequate treatment of relativity. Our calculations are based on the eXact 2-Component molecular-mean field (X2Cmmf) Hamiltonian both with wave function methods and range-separated DFT methods. The second part of this thesis simulates X-ray spectroscopy, where one probes the core region of a molecule. In the core region relativity plays a very significant role. Removal and excitation of electrons from that region involve various processes, which are beyond a mean-field description. We have studied L-edge spectroscopy of the isoelectronic series: UO22+, UNO+, and UN2, where spin-orbit coupling plays a major role. For the theory we have considered single reference open-shell MP2 and Time Dependent Density functional Theory (TDDFT). In another work, we have studied K-edge spectroscopy of the H2X (X= O, S, Se, Te) and XH3 (X= N, P, As) series as well as N2, N2O2 molecules. For this study spin-orbit coupling is less important, therefore, we have treated them with the Spin-Free (SF) DC Hamiltonian. Some of the systems considered in this work are Multi-Reference in nature; we have used Unitary Group Adapted (UGA) State Universal Multi-reference Coupled Cluster (UGA-SUMRCC) theory as a correlation method. In the third and major part of the thesis, the thrust is again on relativity and correlation, but for the calculation of molecular electric and magnetic properties. We have developed and implemented a module for the calculation of expectation values at the 4-component Relativistic Single Reference Coupled Cluster level. Properties that probe the electron density near (heavy) nuclei, such as Electron Paramagnetic Resonance (EPR) parameters, electric field gradients and parity non-conservation (PNC) in chiral molecules are ideally suited for the application of this method. However, we have only studied PNC so far. This module in the DIRAC software for relativstic molecular calculations provides a convenient framework for the implementation of relativistic CC methods employing double group and permutation symmetry very efficiently. In the near future we therefore target the implementation of Linear Response CC for the calculation of excitation energies and second-order molecular properties such as NMR parameters.

This dissertation describes the implementation of the molecular electronic structure calculations with an implicit solvent model using coupled-cluster theory. The theory for and the implementation of the solvent reaction field method (SCRF) and the reference interaction site model (RISM) at the coupled-cluster singles and doubles (CCSD) are presented. In the SCRF model a solute molecule is placed in a spherical cavity, and the outer solvent is represented by a dielectric continuum, which is characterized by the dielectric constant of the solvent. The reaction field is introduced to the system by using the multipole moment expansion of the electronic structure of the solute molecule and the dielectric constant. The SCRF method has been used to calculate the conformational equilibrium and the rotational barriers of 1,2-dichloroethane in vacuum and in different solvents. The calculated results are compared with experimental values. In addition, the solvent effects on the energetics of the mechanism of nitration of benzene are reported using the implemented CCSD-SCRF model. The idea of RISM is to replace the reaction field in continuum models by a microscopic expression in terms of the site-site radial distribution functions between solute and solvent, which can be calculated from the RISM integral equations. The statistical solvent distribution around the solute is determined based on the electronic structure of the solute, while the electronic structure of solute is influenced by the surrounding solvent distribution. Therefore, the wave function and the RISM equations are solved self-consistently with CCSD. Pair correlation functions, partial atomic charges, and solvation free energies of water and N-methylacetamide are calculated in liquid water using proposed theory. Both the CC-SCRF and CC-RISM methods have been implemented in a developmental version of the Q-Chem 3.2 quantum chemistry package.

No description available.

De nombreux noyaux atomiques et hypernoyaux se modélisent comme des structures à trois corps. C'est le cas, par exemple, de noyaux à halo, comme 6He, ou de noyaux stables, comme 12C et 9Be. <p>En effet, 6He se caractérise comme un système à trois corps, formé d'un coeur (une particule alpha) et de deux neutrons de valence faiblement liés. Le noyau de 12C peut s'étudier comme un système lié formé de trois particules alphas, tandis que 9Be peut être décrit comme la liaison de deux particules alphas et d'un neutron.<p><p>Dans les exemples précédents, les particules alphas sont des amas de nucléons. Elles possèdent donc une structure interne dont il faut tenir compte en raison du principe de Pauli.<p><p>Les modèles les plus réalistes pour décrire les structures à trois corps sont les modèles "microscopiques". Ces modèles prennent en compte explicitement tous les nucléons et respectent exactement le principe d'antisymétrisation de Pauli. Cependant, l'application de ces modèles est fortement limitée en pratique, car ils exigent de trop nombreux et trop longs calculs.<p>Par conséquent, pour simplifier considérablement les calculs et permettre l'étude des structures à trois corps, des modèles moins détaillés, de type "semi-microscopiques", sont également développés. Dans ces modèles, on représente les amas de nucléons comme de simples particules ponctuelles. Dans ce cas, la modélisation consiste à construire les potentiels effectifs entre les amas, puis à les employer dans les modèles à trois corps.<p><p>Dans ce travail, nous avons développé les modèles "semi-microscopiques à trois corps". Les potentiels effectifs entre amas sont directement déduits des forces entre nucléons (selon la RGM à 2 corps). Ces potentiels sont "non-locaux", et dépendent des énergies des amas qui interagissent. Ils permettent de simuler le principe de Pauli et les échanges de nucléons entre les amas. La dépendance en l'énergie se révèle être un inconvénient dans les modèles à trois corps. Les potentiels effectifs sont par conséquent transformés en de nouveaux potentiels (non-locaux) indépendants de l'énergie, bien adaptés aux modèles à trois corps. Les modèles "semi-microscopiques" sont beaucoup plus simples et plus rapides que les modèles "microscopiques". Ils fournissent les fonctions d'onde des états liés à trois corps des noyaux légers et hypernoyaux. Cela permet d'une part de comprendre les propriétés spectroscopiques nucléaires, et d'autre part, cela ouvre la voie pour de futurs modèles de réactions nucléaires impliquant les structures à trois corps.<p><p>/<p><p>Several atomic nuclei and hypernuclei can be modelled as three-body structures: e.g. two-neutron halo nuclei, such as 6He, and other nuclei, such as 12C and 9Be.<p>Indeed 6He can be represented as a three-body system, made up of a core (an alpha particle) and two weakly bound valence neutrons. The 12C nucleus can be studied as a bound system formed by three alpha particles, while the 9Be nucleus can be described as the binding of two alpha particles and one neutron.<p><p>In these typical examples, the alpha particles are clusters of nucleons. They have an internal structure that must be taken into account because of the Pauli principle.<p><p>The most realistic models are the "microscopic models". In these models, all the nucleons are taken into account, and the Pauli antisymmetrisation principle is fully respected. However, the application of the "microscopic models" is limited in practice, because they require too many laborious calculations.<p>Therefore, in order to greatly simplify the calculations, "semi-microscopic models" are developed. In those models, the clusters of nucleons are treated as ("structureless") pointlike particles. The models then consist in determining the effective potentials between the clusters, and in using them in three-body models.<p><p>In the present work, we have developed "semi-microscopic models". The effective potentials between the clusters are directly obtained from the interactions between nucleons (according to the two-cluster RGM). These potentials are "nonlocal", and depend on the energy of the interacting clusters. The non-locality is a direct consequence of the Pauli principle and the exchanges of nucleons between the clusters. The energy-dependence of the potentials turns out to be a drawback in three-body models. Therefore, the effective potentials are transformed into energy-independent potentials, which can be used in three-body models. The "semi-microscopic models" are much simpler and faster than the "microscopic models". They provide the three-body bound-state wave functions (i.e. the spectroscopic properties and the structure) of light nuclei and hypernuclei. Such wave functions are also the basic ingredient that will be used in future reactions models. / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

科学研究費補助金 研究種目:一般研究(B) 課題番号:01470008 研究代表者:平尾 公彦 研究期間:1989-1990年度