Iron and cobalt

The primary focus of this dissertation is the advancement of the correlation consistent composite approach (ccCA) methodology from its original formulation to the current implementation. Although for large main group test sets which contained both first- (Li-Ne) and second-row (Na-Ar) species ccCA produced chemical accuracy (generally estimated as a deviation of ~1 kcal mol-1 from reliable experiment), the second-row species were smaller in molecular size in comparison to their corresponding first-row species. Previous theoretical work has shown that the accuracy for theoretical calculations involving second-row species (specifically sulfur-containing species) are more basis set dependent than first-row species. Therefore, an analysis of the accuracy of ccCA for sulfur-containing species is warranted. The ccCA methodology is used to evaluate both enthalpies of formation and bond dissociation energies of sulfur-containing species as well as examine isomerization energies for three sets of sulfur-containing isomers. During the testing of ccCA for sulfur-containing species two observations were made which led to further investigations. First, there is no agreement between different theoretical methodologies on the lowest energetic isomer between SNO and NSO. In fact, G3 and G3B3 which differ only by the geometry of the single-point calculations do not agree on the lowest isomer. For this reason, larger, more complete theoretical treatments of SNO and NSO are investigated. Second, for open-shell sulfur-containing systems the accuracy of the ccCA methodology begins to degrade when spin-contamination becomes non-negligible. Therefore, we investigate the accuracy of the ccCA methodology when spin-contamination is removed from the wavefunction. Finally, the ccCA methodology is utilized in a multilayer ONIOM approach as the high level of theory in conjunction with density functional theory as the low level for the C-H bond dissociation energies of anthracene and fluorene analogues.

Submitted by Edineia Teixeira (edineia.teixeira@unioeste.br) on 2018-02-21T13:51:28Z No. of bitstreams: 2 Iara_Lazzarin2016.pdf: 1672433 bytes, checksum: 40cbdcab03c3030f56a6ab183d9f36e9 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-02-21T13:51:28Z (GMT). No. of bitstreams: 2 Iara_Lazzarin2016.pdf: 1672433 bytes, checksum: 40cbdcab03c3030f56a6ab183d9f36e9 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2015-12-01 / The present paper is about the study of ethics in chemistry graduation classes from two public universities, located in Paraná’s state western region. The chemistry classes’ syllabus establish, to the chemistry graduate, the pedagogic applications of the knowledge and experiences in the field of chemistry and alikes, in the professional acting as an educator in the national elementary education. So, the students’ initial formation is determinant to the development of skills that are required in the classroom. Therefore is necessary that beyond the specifics field subjects, there’s concomitantly discussions about topics like character, ethics and moral. This study has for its main purpose the analysis of the chemistry graduation classes’ coordinators, teachers and students understanding about the study and reflection about ethical principles that should be approached during the initial formation of the chemistry teachers. The present paper was written in a qualitative and quantitative research perspective, which the methodological course used was the documental research, which analyzed laws and basic guidelines of the chemistry discipline, the politic pedagogical projects and syllabus. The field research was done through interviews with the coordinators and teachers of the classes, and the students answered a questionnaire which contained open and closed questions. The results points to a small amount of hours destined to the ethics study in the analyzed classes and to a small reference to subjects that approach ethics in the classes’ syllabus. The results indicate also the necessity of implementing new structures to these courses, in a way that the insertion of subjects related to ethic are includes in the disciplines. Such attitude would allow to develop improve necessary skills to the reflection concerning the study of ethics on the students, aiming the preparation to act in the educational system that embraces responsibility, solidarity and citizenship aspects in the formation process of the new generations / O presente trabalho trata do estudo da Ética nos Cursos de Graduação de Licenciatura em Química de duas instituições públicas de educação superior localizadas na região oeste do Paraná. As Diretrizes Curriculares para Cursos de Química na modalidade de graduação estabelecem, para o licenciado em Química, a aplicação pedagógica do conhecimento e experiências de Química e de áreas afins na atuação profissional como educador na educação básica nacional. Logo, a formação inicial desses estudantes de ensino superior é uma fase determinante para o desenvolvimento de habilidades que serão requeridas em sala de aula quando do futuro exercício da docência para a qual serão habilitados legalmente. Por isso é necessário que, além dos conteúdos específicos da área, haja concomitantemente discussões acerca de temas como caráter, ética e moral. Então a presente pesquisa tem como objetivo central a análise da compreensão da visão dos coordenadores, dos docentes e dos discentes dos Cursos de Química/Licenciatura no que tange ao estudo e à reflexão sobre princípios éticos que deveriam ser abordados durante a formação inicial dos professores de Química. Este trabalho foi escrito numa perspectiva de pesquisa qualitativa e quantitativa, sendo o percurso metodológico realizado pela pesquisa documental, a qual analisou as leis e as diretrizes de base da disciplina de Química, os projetos político- pedagógicos e as grades curriculares desses cursos. A pesquisa de campo foi realizada mediante de entrevistas com os coordenadores e os docentes dos cursos e os alunos responderam a um questionário que continha questões abertas e fechadas. Os resultados da pesquisa apontam para a diminuta carga horária destinada ao estudo da Ética nos cursos analisados e para a pequena referência a conteúdos que tratam de Ética nas ementas curriculares dos cursos. Os resultados indicam ainda para a necessidade de implementação de novas estruturações nos cursos, de modo que a inserção de conteúdos relativos à Ética esteja contemplados nas disciplinas. Tal postura permitiria desenvolver/aprimorar habilidades nos graduandos necessárias para a reflexão do estudo da Ética, visando à preparação para a atuação no sistema educacional, pois a docência necessariamente contempla aspectos de responsabilidade, de solidariedade e de cidadania no processo de formação das novas gerações.