This study addresses the structure and the bonding in the family of tetrahedral boranes. The specific molecules studied are the series B4X4 (X=H, F, Br, Cl, I), the series B4BrCl3, B4Br2Cl2, and B4Br3Cl and tetra-tert-butyl-tetraborane, t-Bu4B4. The research presented herein employs the Hartree-Fock Self Consistent Field (HFSCF), the Moller-Plesset second-order perturbation theory (MP2), and the Density Function Theory (DFT). A variety of basis sets was employed. Our calculations are the first theoretical studies of B4Br4, B4I4, B4BrCl3, B4Br2Cl2, and B4Br3Cl, and are also the first calculations for the D4h structures of any of these molecules, except for B4H4. These results were compared with experimental results, where such comparisons can be made. The most energetically stable structure for all the B4X4 and B4BrnClm molecules has symmetry Td.

A bibliometric study was carried out to identify the main innovations and shortcomings pointed out by scientific research on impact assessment (IA). Out of 1,547 articles published between 1990 and 2015 in two leading journals, IAPA and EIAR, 381 were reviewed for their contents related to new methodological approaches or proposals for improving practice. It was found that innovations and gaps are predominantly treated disregarding IA\'s theoretical basis. We suggest that IA core values shall always guide innovation. It is proposed that the theoretical boundaries of an IA System shall be previously stablished when discussing innovation. The information systematized through a bibliometric approach allowed to propose a framework that correlates IA theoretical foundations with innovation options in a vertical integration way. / Um estudo bibliométrico foi desenvolvido para identificar as principais inovações e lacunas apontadas pela pesquisa científica em avaliação de impactos (AI). Dos 1.547 artigos publicados entre 1990 e 2015 nos dois periódicos de maior relevância na área, o IAPA e o EIAR, 381 artigos tiveram seus conteúdos analisados em relação a novas abordagens metodológicas ou propostas para melhoria da prática. Verificou-se que as inovações e lacunas são tratadas predominantemente desconsiderando a base teórica de AI. Sugerimos que os valores fundamentais da avaliação de impactos devem sempre orientar a inovação. Propõe-se que as fronteiras teóricas de um Sistema AI sejam estabelecidas previamente ao se discutir a inovação. A informação sistematizada através de uma abordagem bibliométrica permitiu propor uma estrutura que correlaciona os fundamentos teóricos da avaliação de impactos com as opções de inovação.

Estudos pioneiros na década de 1970 com cálculos ab initio inauguraram o campo da química quântica relativística computacional. Desde então, também devido ao crescimento exponencial da capacidade computacional, a aplicação de Hamiltonianos relativísticos em cálculos de química teórica tem se tornado cada vez mais frequente. No entanto, o desenvolvimento de conjuntos de funções de base para estes cálculos não seguiu no mesmo ritmo. Após décadas, as melhores opções disponíveis ainda apresentam certas limitações técnicas, como sinais de prolapso variacional. Desta forma, o objetivo deste trabalho foi a geração de eficientes conjuntos relativísticos de funções de base Gaussianas para aplicação em cálculos ab initio correlacionados. Usou-se então de uma versão polinomial do método da coordenada geradora Dirac-Fock para elaboração de um conjunto primitivo de funções otimizadas variacionalmente livres de prolapso. Funções de correlação/polarização e funções difusas foram adicionadas em acordo com uma incrementação do tipo quadruple-ζ. Estas funções foram escolhidas através do tratamento multi-referencial de interação de configurações com o Hamiltoniano Dirac-Coulomb. Cálculos moleculares de propriedades fundamentais atestaram a qualidade destes conjuntos, denominados RPF-4Z, em comparação com outras bases relativísticas bastante utilizadas na literatura. Adicionalmente, momentos de quadrupolo nuclear de isótopos de bismuto e potássio e uma curva de energia potencial do dímero de rádio foram obtidos com estes conjuntos. Ao prover funções de base que retornam resultados comparáveis a outros conjuntos relativísticos disponíveis de qualidade quadruple-ζ, mas com uma significativa redução na demanda computacional, espera-se que as bases RPF-4Z se traduzam em um grande avanço na área. / Pioneering studies with ab initio calculations from the 1970s gave rise to the computational relativistic quantum chemistry field. Since then, also due to the exponential growth in computational resources, the application of relativistic Hamiltonians in theoretical chemistry calculations has become more common. However, the development of basis sets to be used in such calculations have presented its struggles. After decades, technical limitations, such as the variational prolapse issue still persist. Hence, the aim of the present thesis was the development of efficient relativistic Gaussian basis sets to be applied in correlated ab initio calculations. In order to do that, a polynomial version of the generator coordinate Dirac-Fock method has been applied to obtain variationally optimized primitive sets that are free of prolapse. Correlating/polarization functions, as well as diffuse ones, were added to these sets in a quadruple-ζ type of increment. Such functions were chosen by means of the Dirac-Coulomb multi-reference configuration interaction treatment. Molecular calculations of fundamental properties have attested the high quality of the designated RPF-4Z sets in comparison with other well-known relativistic sets. Furthermore, nuclear electric quadrupole moments of bismuth and potassium isotopes and a potential energy curve of the radium dimer were also analyzed. Since these generated sets are as accurate as commonly used relativistic quadruple-ζ sets already available, but with the advantage of a reduced computational demand, the RPF-4Z sets are expected to represent a great advance in the field.

Lau Kai-Chung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references. / Abstracts in English and Chinese. / Abstract / Acknowledgements / Table of Contents / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- The Gaussian-2 Method / Chapter 1.2 --- The G2 Method with Reduced M φller-Plesset Order and Basis Set / Chapter 1.3 --- The Gaussian-3 Method / Chapter 1.4 --- Our Modified G2 Methods / Chapter 1.5 --- Calculation of Thermodynamical Data / Chapter 1.6 --- Scope of the Thesis / Chapter 1.7 --- Remark on the Location of Transition Structures / Chapter 1.8 --- References / Chapter Chapter 2 --- A Gaussian-2 Study of the [C2H5O-] Potential Energy Surface and the Fragmentation Pathways of the Ethoxide Anion --- p.7 / Chapter 2.1 --- Introduction / Chapter 2.2 --- Theoretical Methods / Chapter 2.3 --- Results and Discussion / Chapter 2.3.1 --- Stable Isomers and TSs for the [C2H50-] Anions / Chapter 2.3.2 --- Fragmentation Pathways of the Ethoxide Anion (1-) / Chapter 2.4 --- Conclusions / Chapter 2.5 --- Publication Note / Chapter 2.6 --- References / Chapter Chapter 3 --- A Gaussian-2 Study of Isomeric C2H2N and C2H2N+ --- p.20 / Chapter 3.1 --- Introduction / Chapter 3.2 --- Theoretical Methods / Chapter 3.3 --- Results and Discussion / Chapter 3.3.1 --- The C2H2N and C2H2N+ Isomers / Chapter 3.3.2 --- The Cyanomethyl Radical (1) and Cation (1+) / Chapter 3.3.3 --- The Isocyanomethyl Radical (2) and Cation (2+) / Chapter 3.3.4 --- The lH-Azirinyl Radical (5) and Cation (5+) / Chapter 3.3.5 --- Other C2H2N and C2H2N+ Isomers / Chapter 3.3.6 --- The Unidentified C2H2N Isomer Formed in N + CH=CH2 / Chapter 3.4 --- Conclusions / Chapter 3.5 --- Publication Note / Chapter 3.6 --- References / Chapter Chapter 4 --- A Gaussian-2 Study of the Photoionization and Dissociative Photoionization Channels of Ethylene Oxide --- p.35 / Chapter 4.1 --- Introduction / Chapter 4.2 --- Theoretical Methods / Chapter 4.3 --- Results and Discussion / Chapter 4.3.1 --- Bond Cleavage Reactions / Chapter 4.3.2 --- Dissociation Channels Involving Transition Structure(s) / Chapter 4.4 --- Conclusions / Chapter 4.5 --- Publication Note / Chapter 4.6 --- References / Chapter Chapter 5 --- A Gaussian-2 Study of the Photoionization and Dissociative Photoionization Channels of Propylene Oxide --- p.47 / Chapter 5.1 --- Introduction / Chapter 5.2 --- Theoretical Methods / Chapter 5.3 --- Results and Discussion / Chapter 5.3.1 --- Bond Cleavage Reactions / Chapter 5.3.2 --- Dissociation Channels Involving Transition Structure(s) / Chapter 5.4 --- Conclusions / Chapter 5.5 --- Publication Note / Chapter 5.6 --- References / Chapter Chapter 6 --- A Gaussian-3 Study of the Thermochemistry of Chlorofluoromethanes (CFnCl4-n) and Their Cations (CFnCl4_n+)， n =0-4 --- p.61 / Chapter 6.1 --- Introduction / Chapter 6.2 --- Theoretical Methods / Chapter 6.3 --- Results and Discussions / Chapter 6.3.1 --- Heats of Formation of Chlorofluoromethanes and Their Cations / Chapter 6.3.2 --- Ionization Energies of Chlorofluoromethanes / Chapter 6.3.3 --- Proton Affinities of Chlorofluoromethanes / Chapter 6.4 --- Conclusions / Chapter 6.5 --- Publication Note / Chapter 6.6 --- References / Chapter Chapter 7 --- "A Gaussian-2 and Gaussian-3 Study of the Energetics and Structures of Cl2On and Cl2On+, n = 1，4, 6，and7" --- p.69 / Chapter 7.1 --- Introduction / Chapter 7.2 --- Theoretical Methods / Chapter 7.3 --- Results and Discussion / Chapter 7.3.1 --- Cl20 and Cl20+ / Chapter 7.3.2 --- Cl204 and Cl204+ / Chapter 7.3.3 --- Cl206 and Cl206+ / Chapter 7.3.4 --- Cl207 and Cl207+ / Chapter 7.4 --- Conclusions / Chapter 7.5 --- Publication Note / Chapter 7.6 --- References / Chapter Chapter 8 --- Conclusions --- p.81 / Chapter Appendix A --- The Gaussian-n (n = 1 - 3) Theoretical Models --- p.82 / Chapter A.1 --- The G1 and G2 theories / Chapter A.2 --- The G2(MP2) theory / Chapter A.3 --- "The G2(MP2,SVP) theory" / Chapter A.4 --- The G3 theory / Chapter Appendix B --- "Calculation of Enthalpy at 298 K, H298" --- p.86

Law Chi-Kin. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references. / Abstracts in English and Chinese. / Abstract --- p.i / Acknowledgements --- p.iii / Table of Contents --- p.iv / List of Tables --- p.vi / List of Figures --- p.viii / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- The Gaussian´ؤ3 Method --- p.1 / Chapter 1.2 --- The G3 Method with Reduced Mφller-Plesset Order and Basis Set --- p.2 / Chapter 1.3 --- The Gaussian-3X Method --- p.2 / Chapter 1.4 --- Calculation of Thermodynamical Data --- p.3 / Chapter 1.5 --- Remark on the Location of Equilibrium and Transition Structures --- p.3 / Chapter 1.6 --- Natural Bond Orbital (NBO) Analysis --- p.4 / Chapter 1.7 --- Scope of the Thesis --- p.4 / Chapter 1.8 --- References --- p.5 / Chapter Chapter 2 --- Gaussian´ؤ3 Heats of Formation for (CH)6 Isomers --- p.6 / Chapter 2.1 --- Introduction --- p.6 / Chapter 2.2 --- Methods of Calculation and Results --- p.7 / Chapter 2.3 --- Discussion --- p.9 / Chapter 2.4 --- Conclusion --- p.11 / Chapter 2.5 --- Publication Note --- p.12 / Chapter 2.6 --- References --- p.12 / Chapter Chapter 3 --- A Gaussian-3 Investigation of N7 Isomers --- p.14 / Chapter 3.1 --- Introduction --- p.14 / Chapter 3.2 --- Computational Method and Results --- p.16 / Chapter 3.3 --- Discussion --- p.16 / Chapter 3.4 --- Conclusion --- p.24 / Chapter 3.5 --- Publication Note --- p.24 / Chapter 3.6 --- References --- p.24 / Chapter Chapter 4 --- A Gaussian-3 Study of N7+ and N7- Isomers --- p.27 / Chapter 4.1 --- Introduction --- p.27 / Chapter 4.2 --- Computational Method and Results --- p.29 / Chapter 4.3 --- Discussion --- p.30 / Chapter 4.3.1 --- The N7+ isomers --- p.30 / Chapter 4.3.2 --- The N7- isomers --- p.37 / Chapter 4.4 --- Conclusion --- p.41 / Chapter 4.5 --- Publication Note --- p.41 / Chapter 4.6 --- References --- p.41 / Chapter Chapter 5 --- "Thermochemistry of Chlorine Fluorides ClFn, n = 1-7, and Their Singly Charged Cations and Anions: A Gaussian-3 and Gaussian-3X Study" --- p.45 / Chapter 5.1 --- Introduction --- p.45 / Chapter 5.2 --- Methods of Calculations --- p.47 / Chapter 5.3 --- Results and Discussion --- p.48 / Chapter 5.3.1 --- Comparison of the G3 and G3X methods --- p.48 / Chapter 5.3.2 --- Assessments of the experimental results --- p.54 / Chapter 5.3.3 --- "Bond dissociation energies of ClFn, ClFn+, and ClFn-" --- p.57 / Chapter 5.3.4 --- Summary of the thermochemical data --- p.58 / Chapter 5.4 --- Conclusion --- p.59 / Chapter 5.5 --- Publication Note --- p.60 / Chapter 5.6 --- References --- p.60 / Chapter Chapter 6 --- A Gaussian-3 Study of the Photoionization and Dissociative Photoionization Channels of Dimethyl Sulfide --- p.63 / Chapter 6.1 --- Introduction --- p.63 / Chapter 6.2 --- Methods of Calculations --- p.64 / Chapter 6.3 --- Results and Discussion --- p.64 / Chapter 6.3.1 --- Bond cleavage reactions --- p.67 / Chapter 6.3.2 --- Dissociation channels involving transition structures --- p.68 / Chapter 6.4 --- Conclusion --- p.70 / Chapter 6.5 --- Publication Note --- p.70 / Chapter 6.6 --- References --- p.70 / Chapter Chapter 7 --- "Theoretical Study of the Electronic Structures of Carbon and Silicon Nanotubes, Carbon and Silicon Nanowires" --- p.72 / Chapter 7.1 --- Introduction --- p.72 / Chapter 7.2 --- Models and Computational Methods --- p.74 / Chapter 7.3 --- Results and Discussion --- p.75 / Chapter 7.4 --- Conclusion --- p.87 / Chapter 7.5 --- Publication Note --- p.87 / Chapter 7.6 --- References --- p.87 / Chapter Chapter 8 --- Conclusion --- p.90 / Appendix A --- p.91 / Appendix B

Cheng Mei-Fun. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2003. / Includes bibliographical references. / Abstracts in English and Chinese. / Abstract --- p.i / Acknowledgements --- p.iii / Table of Contents --- p.iv / List of Tables --- p.vi / List of Figures --- p.viii / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- The Gaussian-3 Method --- p.1 / Chapter 1.2 --- The G3 Method with Reduced Mφller-Plesset Order and Basis Set --- p.2 / Chapter 1.3 --- Density Functional Theory (DFT) --- p.3 / Chapter 1.4 --- Calculation of Thermodynamical Data --- p.3 / Chapter 1.5 --- Remark on the Location of Transition Structures --- p.3 / Chapter 1.6 --- Natural Bond Orbital (NBO) Analysis --- p.4 / Chapter 1.7 --- Scope of the Thesis --- p.4 / Chapter 1.8 --- References --- p.5 / Chapter Chapter 2 --- Heats of Formation for the Azine Series: A Gaussian-3 Study --- p.7 / Chapter 2.1 --- Introduction --- p.7 / Chapter 2.2 --- Methods of Calculation and Results --- p.8 / Chapter 2.3 --- Discussion --- p.8 / Chapter 2.4 --- Conclusion --- p.9 / Chapter 2.5 --- Publication Note --- p.10 / Chapter 2.6 --- References --- p.10 / Chapter Chapter 3 --- Heats of Formation for Some Boron Hydrides: A Gaussian-3 Study --- p.16 / Chapter 3.1 --- Introduction --- p.16 / Chapter 3.2 --- Methods of Calculation and Results --- p.18 / Chapter 3.3 --- Discussion --- p.19 / Chapter 3.4 --- Conclusion --- p.21 / Chapter 3.5 --- Publication Note --- p.21 / Chapter 3.6 --- References --- p.21 / Chapter Chapter 4 --- Structural and Energetics Studies of Tri- and Tetra-tert-butylmethane --- p.30 / Chapter 4.1 --- Introduction --- p.30 / Chapter 4.2 --- Methods of Calculation and Results --- p.32 / Chapter 4.3 --- Discussion --- p.34 / Chapter 4.3.1 --- Mono-tert-butylmethane --- p.34 / Chapter 4.3.2 --- Di-tert-butylmethane --- p.35 / Chapter 4.3.3 --- Tri-tert-butylmethane --- p.37 / Chapter 4.3.4 --- Tetra-tert-butylmethane --- p.38 / Chapter 4.4 --- Conclusion --- p.39 / Chapter 4.5 --- Publication Note --- p.40 / Chapter 4.6 --- References --- p.40 / Chapter Chapter 5 --- A Computational Study of the Diels-Alder Reactions Involving Acenes: Reactivity and Aromaticity --- p.49 / Chapter 5.1 --- Introduction --- p.49 / Chapter 5.2 --- Methods of Calculation and Results --- p.50 / Chapter 5.3 --- Discussion --- p.51 / Chapter 5.4 --- Conclusion --- p.53 / Chapter 5.5 --- Publication Note --- p.53 / Chapter 5.6 --- References --- p.53 / Chapter Chapter 6 --- A Computational Study of the Charge- Delocalized and Charge-Localized Forms of the Croconate and Rhodizonate Dianions --- p.65 / Chapter 6.1 --- Introduction --- p.65 / Chapter 6.2 --- Methods of Calculation and Results --- p.67 / Chapter 6.3 --- Discussion --- p.68 / Chapter 6.3.1 --- Charge-Localized Forms of C5052- (C2v) and C6O6 2-(C2v) --- p.68 / Chapter 6.3.2 --- Charge-Delocalized Forms of C5052- (D5h) and C6062- (D6h) --- p.71 / Chapter 6.4 --- Conclusion --- p.72 / Chapter 6.5 --- Publication Note --- p.73 / Chapter 6.6 --- References --- p.74 / Chapter Chapter 7 --- Conclusion --- p.89 / Appendix A --- p.90 / Appendix B --- p.92

Com a maior ênfase nas questões ambientais nos últimos anos, tanto em âmbito internacional, quanto em âmbito nacional, diversas são as medidas adotadas visando o desenvolvimento sustentável. Dentre elas a regulação ambiental, a qual é capaz de impor medidas de forma preventiva, mitigatória e compensatória, frente às atividades com impactos negativos ao meio ambiente. Neste estudo, dá-se ênfase às medidas compensatórias, mecanismos capazes de amenizar impactos com efeitos negativos ao meio ambiente não passíveis de serem mitigados por medidas preventivas ou reparatórias, cuja aplicação apresenta diversas discussões, dentre elas a incerteza dos fundamentos que as justificam e seu aproveitamento para o processo desenvolvimento. Dessa forma, este estudo objetiva analisar as medidas compensatórias por meio de seus fundamentos normativos e jurídicos, bem como seu papel para o desenvolvimento nacional, questionando-se se o aumento da regulação ambiental, por meio de tais medidas, favorece o processo de desenvolvimento sob o enfoque da segurança jurídica dos empreendedores submetidos às mesmas. Estudo este que se justifica pelo fato da regulação ambiental se mostrar ainda incipiente na aplicação das medidas compensatórias, com questionamentos em relação aos seus fundamentos, aos aspectos jurídicos envolvidos em sua aplicação, além de repercutir em aspectos econômicos, com desdobramentos ao empreendedor privado e ao próprio Estado na compatibilização de interesses públicos e privados. Assim, para atingir os objetivos acima, como linha central deste estudo foram utilizadas, de forma subsidiária, a análise de mecanismos econômicos associados aos de comando e controle e, de forma principal, as teorias de desenvolvimento de Amartya Sen e Douglass North, já como marco teórico se destacam as diversas teorias quanto a natureza jurídica das medidas compensatórias e da compensação ambiental, no qual optou-se pela análise dogmática jurídica, com o método interpretativo/dedutivo com enfoque na análise qualitativa de tal instituto. Como resultado chegou-se a: falta de uniformização legal; dificuldade de se estabelecer uma vinculação ou não com o impacto ambiental do empreendimento; ausência de discricionariedade do administrador público; bem como falta de consenso em relação a natureza jurídica de tal instituto. Conclui-se, desse modo, que a problemática envolvendo as medidas compensatórias ambientais possibilita sua análise por meio de teorias desenvolvimentistas, cuja aplicação pode ser uma das vias utilizadas para o aperfeiçoamento de sua utilização no processo de desenvolvimento sustentável, uma vez que as discussões puramente jurídicas não têm demonstrado resultados efetivos na aplicação do instituto, além de que as diversas normas concernentes às medidas compensatórias ambientais não são suficientes para dirimir as diversas problemáticas envolvendo tal instituto acima destacado, pontos estes que são fortes fatores de insegurança àqueles submetidos a tais medidas. Assim, as medidas compensatórias, se bem utilizadas a luz das teorias de desenvolvimento, especialmente as de North e Sen, podem contribuir positivamente para no processo de desenvolvimento sustentável, sendo certo que a utilização de mecanismos puramente regulatórios, desassociados de políticas voltadas ao desenvolvimento, não tem demonstrado resultados positivos, não favorecendo a segurança jurídica daqueles submetidos a tais medidas. / With the greatest emphasis on environmental issues in recent years, both internationally and nationally, there are a number of measures taken to achieve sustainable development. Among them, environmental regulation, which is capable of imposing preventive, mitigating and compensatory measures, in the face of activities with negative impacts on the environment. In this study, emphasis is placed on compensatory measures, mechanisms are analyzed that are capable of mitigating impacts with negative effects on the environment that can not be mitigated by preventive or remedial measures, whose application presents several discussions, among them the uncertainty of the justifications and its use for the development process. Thus, this study aims to analyze compensatory measures through their normative and legal bases, as well as their role for national development, questioning whether the increase of environmental regulation, through such measures, favors the development process under the legal certainty of the entrepreneurs submitted to them. This study is justified by the fact that environmental regulation is still incipient in the application of compensatory measures, with questions related to its fundamentals, the legal aspects involved in its application, as well as repercussions on economic aspects, with consequences for the private entrepreneur and the itself in the reconciliation of public and private interests. In order to achieve the above objectives, the main focus of this study was the analysis of the economic mechanisms associated with command and control and, mainly, the development theories of Amartya Sen and Douglass North, the theoretical framework highlights the different theories regarding the legal nature of compensatory measures and environmental compensation, in which the legal dogmatic analysis was chosen, with the interpretive/deductive method with a focus on the qualitative analysis of such institute. As a result, there was a lack of legal standardization; difficulty in establishing a connection or not with the environmental impact of the enterprise; lack of discretion of the public administrator; aas well as a lack of consensus on the legal nature of such an institute. It is concluded, therefore, that the problem of environmental compensatory measures makes possible its analysis through developmental theories, the application of which can be one of the ways used to improve its use in the process of sustainable development, since the purely use of law have not shown effective results in the application of the institute, in addition to the fact that the various norms concerning environmental compensatory measures are not sufficient to solve the various problems involved in this institute, which are strong factors of insecurity for those subject to such measures. Thus, compensatory measures, if well used in the light of developmental theories, especially those of North and Sen, can contribute positively to the process of sustainable development, although the use of purely regulatory mechanisms, disassociated with development policies, has not shown positive results and does not favor the legal certainty of those subject to such measures.

In this research project, the Boundary Element Method (BEM) is developed and formulated for the solution of two-dimensional convection-diffusion-reaction problems. A combined approach with the dual reciprocity boundary element method (DRBEM) has been applied to solve steady-state problems with variable velocity and transient problems with constant and variable velocity fields. Further, the radial integration boundary element method (RIBEM) is utilised to handle non-homogeneous problems with variable source term. For all cases, a boundary-only formulation is produced. Initially, the steady-state case with constant velocity is considered, by employing constant boundary elements and a fundamental solution of the adjoint equation. This fundamental solution leads to a singular integral equation. The conservation laws, usually applied to avoid this integration, do not hold when a chemical reaction is taking place. Then, the integrals are successfully computed using Telles' technique. The application of the BEM for this particular equation is discussed in detail in this work. Next, the steady-state problem for variable velocity fields is presented and investigated. The velocity field is divided into an average value plus a perturbation. The perturbation is taken to the right-hand-side of the equation generating a non-homogeneous term. This nonhomogeneous equation is treated by utilising the DRM approach resulting in a boundary-only equation. Then, an integral equation formulation for the transient problem with constant velocity is derived, based on the DRM approach utilising the fundamental solution of the steady-state case. Therefore, the convective terms will be encompassed by the fundamental solution and lie within the boundary integral after application of Greens's second identity, leaving on the right-hand-side of the equation a domain integral involving the time-derivative only. The proposed DRM method needs the time-derivative to be expanded as a series of functions that will allow the domain integral to be moved to the boundary. The expansion required by the DRM uses functions which take into account the geometry and physics of the problem, if velocity-dependent terms are used. After that, a novel DRBEM model for transient convection-diffusion-reaction problems with variable velocity field is investigated and validated. The fundamental solution for the corresponding steady-state problem is adopted in this formulation. The variable velocity is decomposed into an average which is included into the fundamental solution of the corresponding equation with constant coefficients, and a perturbation which is treated using the DRM approximation. The mathematical formulation permits the numerical solution to be represented in terms of boundary-only integrals. Finally, a new formulation for non-homogeneous convection-diffusion-reaction problems with variable source term is achieved using RIBEM. The RIM is adopted to convert the domain integrals into boundary-only integrals. The proposed technique shows very good solution behaviour and accuracy in all cases studied. The convergence of the methods has been examined by implementing different error norm indicators and increasing the number of boundary elements in all cases. Numerical test cases are presented throughout this research work. Their results are sufficiently encouraging to recommend the use of the techniques developed for solution of general convection-diffusion-reaction problems. All the simulated solutions for several examples showed very good agreement with available analytical solutions, with no numerical problems of oscillation and damping of sharp fronts.

Lau Kai-Chi. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references. / Abstracts in English and Chinese. / Abstract --- p.i / Acknowledgements --- p.iii / Table of Contents --- p.iv / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- The Gaussian´ؤ3 Method --- p.1 / Chapter 1.2 --- The G3 Method with Reduced MΦ ller-Plesset Order and Basis Set --- p.2 / Chapter 1.3 --- The Gaussian-3X Method --- p.2 / Chapter 1.4 --- The Modified G2 Method --- p.3 / Chapter 1.5 --- Calculation of Thermodynamical Data --- p.3 / Chapter 1.6 --- Remark on the Location of Transition Structures --- p.4 / Chapter 1.7 --- Scope of the Thesis --- p.4 / Chapter 1.8 --- References --- p.4 / Chapter Chapter 2 --- "A Gaussian-2 and Gaussian-3 Study of Alkoxide Anion Decompositions. I. H2 and CH4 Eliminations of the Methoxide, Ethoxide, i-Propoxide, and t-Butoxide Anions" --- p.6 / Chapter 2.1 --- Introduction --- p.6 / Chapter 2.2 --- Methods of Calcuations --- p.7 / Chapter 2.3 --- Results and Discussion --- p.8 / Chapter 2.3.1 --- Nature of ion-neutral complex --- p.8 / Chapter 2.3.2 --- Initial bond cleavage of alkoxide anions --- p.9 / Chapter 2.3.3 --- Dissociation of alkoxide anions --- p.10 / Chapter 2.4 --- Conclusions --- p.23 / Chapter 2.5 --- Publication Note --- p.25 / Chapter 2.6 --- References --- p.25 / Chapter Chapter 3 --- A Gaussian-2 and Gaussian-3 Study of Alkoxide Anion Decompositions. II. Alkane Eliminations of (CH3)2(C2H5)CO- and (i-Pr)(C2H5)2CO- --- p.28 / Chapter 3.1 --- Introduction --- p.28 / Chapter 3.2 --- Methods of Calculations --- p.29 / Chapter 3.3 --- Results and Discussion --- p.29 / Chapter 3.3.1 --- Initial bond cleavage of alkoxide anions --- p.30 / Chapter 3.3.2 --- Dissociation of alkoxde anions --- p.31 / Chapter 3.3.3 --- General dissociation mechanism of alkoxide anions --- p.35 / Chapter 3.4 --- Conclusions --- p.37 / Chapter 3.5 --- References --- p.37 / Chapter Chapter 4 --- A Gaussian-3 Study of the Photoionization and Dissociative Photoionization Channels of Dimethyl Disulfide --- p.40 / Chapter 4.1 --- Introduction --- p.40 / Chapter 4.2 --- Methods of Calculations --- p.41 / Chapter 4.3 --- Results and Discussion --- p.41 / Chapter 4.3.1 --- Bond cleavage reactions --- p.44 / Chapter 4.3.2 --- Dissociation channels involving transition structures --- p.45 / Chapter 4.4 --- Conclusions --- p.48 / Chapter 4.5 --- References --- p.48 / Chapter Chapter 5 --- A Gaussian´ؤ3 Study of the Photodissociation Channels of Propylene Sulfide --- p.50 / Chapter 5.1 --- Introduction --- p.50 / Chapter 5.2 --- Methods of Calculations --- p.51 / Chapter 5.3 --- Results and Discussion --- p.51 / Chapter 5.3.1 --- The dissociation channels involving transition structures --- p.53 / Chapter 5.3.2 --- The dissociations of sulfur atom --- p.56 / Chapter 5.4 --- Conclusions --- p.58 / Chapter 5.5 --- References --- p.59 / Chapter Chapter 6 --- Thermochemistry of Phosphorus Fluorides: A Gaussian´ؤ3 and Gaussian´ؤ3X Study --- p.60 / Chapter 6.1 --- Introduction --- p.60 / Chapter 6.2 --- Methods of Calculations --- p.62 / Chapter 6.3 --- Results and Discussion --- p.62 / Chapter 6.3.1 --- Comparison of the G3 and G3X methods --- p.62 / Chapter 6.3.2 --- Assessments of the experimental results --- p.65 / Chapter 6.4 --- Conclusions --- p.71 / Chapter 6.5 --- References --- p.71 / Chapter Chapter 7 --- Conclusions --- p.74 / Appendix A --- p.75 / Appendix B --- p.78

Resumo: A previsão de carga, em sistemas de energia elétrica, constitui-se numa atividade de grande importância, tendo em vista que a maioria dos estudos realizados (fluxo de potência, despacho econômico, planejamento da expansão, compra e venda de energia, etc.) somente poderá ser efetivada se houver a disponibilidade de uma boa estimativa da carga a ser atendida. Deste modo, visando contribuir para que o planejamento e operação dos sistemas de energia elétrica ocorram de forma segura, confiável e econômica, foi desenvolvida uma metodologia para previsão de carga, a previsão multinodal, que pode ser entendida como um sistema inteligente que considera vários pontos da rede elétrica durante a realização da previsão. O sistema desenvolvido conta com o uso de uma rede neural artificial composta por vários módulos, sendo esta do tipo perceptron multicamadas, cujo treinamento é baseado no algoritmo retropropagação. Porém, foi realizada uma modificação na função de ativação da rede, em substituição à função usual, a função sigmoide, foram utilizadas as funções de base radial. Tal metodologia foi aplicada ao problema de previsão de cargas elétricas a curto-prazo (24 horas à frente) / Abstract: Load forecasting in electric power systems is a very important activity due to several studies, e.g. power flow, economic dispatch, expansion planning, purchase and sale of energy that are extremely dependent on a good estimate of the load. Thus, contributing to a safe, reliable, economic and secure operation and planning this work is developed, which is an intelligent system for multinodal electric load forecasting considering several points of the network. The multinodal system is based on an artificial neural network composed of several modules. The neural network is a multilayer perceptron trained by backpropagation where the traditional sigmoide is substituted by radial basis functions. The methodology is applied to forecast loads 24 hours in advance / Orientador: Carlos Roberto. Minussi / Coorientador: Francisco Villarreal Alvarado / Banca: Anna Diva Plasencia Lotufo / Banca: Maria do Carmo Gomes da Silveira / Banca: Gelson da Cruz Junior / Banca: Edmárcio Antonio Belati / Doutor