Quantum Monte Carlo : some theoretical and numerical studies

In Part I, theoretical derivations for Variational Monte Carlo calculations are compared with results from a numerical calculation of He; both indicate that minimization of the ratio estimate of Evar , denoted EMC ' provides different optimal variational parameters than does minimization of the variance of E MC • Similar derivations for Diffusion Monte Carlo calculations provide a theoretical justification for empirical observations made by other workers. In Part II, Importance sampling in prolate spheroidal coordinates allows Monte Carlo calculations to be made of E for the vdW molecule var He2' using a simplifying partitioning of the Hamiltonian and both an HF-SCF and an explicitly correlated wavefunction. Improvements are suggested which would permit the extension of the computational precision to the point where an estimate of the interaction energy could be made~

Half-sandwich silane complexes of ruthenium and iron : synthesis, structure and application to catalysis

The present thesis describes syntheses, structural studies, and catalytic reactivity of new non-classical silane complexes of ruthenium and iron. The ruthenium complexes CpRu(PPri3)CI(T]2-HSiR3) (1) (SiR3 = SiCh (a), SiClzMe (b), SiCIMe2 (c), SiH2Ph (d), SiMe2Ph (e» were prepared by reactions of the new unsaturated complex CpRu(PPri3)CI with silanes. According to NMR studies and X-ray analyses, the complexes la-c exhibit unusual simultaneous Si··· H and Si··· CI-Ru interactions. The complex CpRu(PPri3)CI was also used for the preparation of the first examples of late transition metal agostic silylamido complexes CpRu(PPri3)(N(T]2-HSiMe2)R) (2) (R= Ar or But), which were characterized by NMR spectroscopy. The iron complexes CpFe(PMePri2)H2(SiR3) (3) (SiR3 = SiCh (a), SiClzMe (b), SiCIMe2 (c), SiH2Ph (d), SiMe2Ph (e» were synthesized by the reaction of the new borohydride iron complex CpFe(PMePri2)(B~) with silanes in the presence NEt3. The complexes 3 exhibit unprecedented two simultaneous and equivalent Si··· H interactions, which was confirmed by X-ray analyses and DFT calculations. A series of cationic ruthenium complexes [CpRu(PR3)(CH3CN)(112-HSiR'3)]BAF (PR3 = PPri 3 (4), PPh3 (5); SiR'3 = SiCh (a), SiClzMe (b), SiClMe2 (c), SiH2Ph (d), SiMe2Ph (e» was obtained by substitution of one of the labile acetonitrile ligands in [CpRu(PR3)(CH3CNh]BAF with sHanes. Analogous complexes [TpRu(PR3)(CH3CN)(T]2 -HSiR' 3)]BAF (5) were obtained by the reaction of TpRu(PR3)(CH3CN)CI with LiBAF in the presence of silanes. The complexes 4-5 were characterized by NMR spectroscopy, and the observed coupling constants J(Si-H) allowed us to estimate the extent of Si-H bond activation in these compounds. The catalytic activity in hydrosilylation reactions of all of the above complexes was examined. The most promising results were achieved with the cationic ruthenium precatalyst [CpRu(PPri3)(CH3CN)2t (6). Complex 6 shows good to excellent catalytic activity in the hydrosilylation of carbonyls, dehydrogenative coupling of silanes with alcohols, amines, acids, and reduction of acid chlorides. We also discovered very selective reduction of nitriles and pyridines into the corresponding N-silyl imines and l,4-dihydropyridines, respectively, at room temperature with the possibility of catalyst recycling. These chemoselective catalytic methods have no analogues in the literature. The reactions were proposed to proceed via an ionic mechanism with intermediate formation of the silane a-complexes 4.

Early Education Foundation: Portuguese Canadian Mothers' Preferences and Choices

The purpose of this study was to explore Portuguese-Canadian mothers' preferences and choices regarding their children's early care and education. The findings revealed that Portuguese-Canadian mothers value early care and education and are conscious of their role in their children's lives. Regardless of the type of care setting, the participants' responses revealed that the caregiver's care, emotion, and responsiveness are most important. More than developing "savvy" children, we need to nourish "happy" children. The study's participants include 9 Portuguese Canadian mothers without any assumption of a hyphenated identity and who have moved away from their immigrant parents' script. They embraced the vision of their children's success and cultivated their vast potential. Their responses revealed that the family, culture, and traditions are important factors in their child's academic and social growth and played a critical role in establishing the foundations for learning. The research study findings showed that the field of early care and education is undergoing a paradigm shift and that other practices, ideologies, and theories are surfacing. This study aimed to help develop a new grounded theory that contributes to a better understanding of this arena. The present findings reveal important issues for further discussion and lay a theoretical and empirical framework for future research in early education and care.

3-O-Demethylation of thebaine and the synthesis of a flacourtia aglycone from benzoic acid.

Two synthetic projects were embarked upon, both fraught with protecting group nuance and reaction selectivity. Transformations of the opiate skeleton remain a valuable tool for the development of new medicines. Thebaine, a biosynthetic intermediate in the expression of morphine, was converted in three steps to oripavine through two parallel modes. Through the use of protecting group manipulations, two irreversible scaffold rearrangements were avoided during aryl methyl ether bond cleavage. This chemistry constitutes a new path in manipulations of the morphinan scaffold through protective groups. A new compound family, the flacourtosides, contains an unusual cyclohexenone fragment. The newly described compounds show in preliminary tests antiviral activity against dengue and chikungunya. This aglycone was approached on three pathways, all beginning with the chemoenzymatic dihydroxylation of benzoic acid. A first attempt from a known vinyl epoxide failed to epimerize and cooperate under deprotective conditions. A second and third attempt made use of a diastereoselective dihydroxylation reaction, which was critical in reaching the correct stereochemistry and oxidation state. The methyl ester of the aglycone was prepared, constituting the first synthesis of the non-trivial natural product framework.

The quality of the mother-child relationship during collaborative problem solving /

The quality of the mother-child relationship was examined in relation to joint planning, maternal teaching strategies, maternal emotional support, mutual positive affect and attachment security. Fifty-five grade five children and their mothers participated in a laboratory session comprised of various activities and completed questionnaires to evaluate attachment security. Joint planning and social problem solving were assessed observationally during an origami task. Problem solving effectiveness was unrelated to maternal teaching strategies, maternal encouragement and mutual positive affect. A marginally significant relationship was found between maternal encouragement and active child participation. Attachment security was found to be significantly related to sharing of responsibility during local planning, but only for child autonomous performance. An examination of conditional probabilities revealed that mutual positive affect did not increase the likelihood of subsequent mother-child dyadic regulation. However, mutual positive affect was found to be significantly related to both active child participation and dyadic regulation. The hypothesis predicting a mediational model was not supported. The implications of these findings in the theoretical and empirical literature were considered and suggestions for future research were made.

Asymmetrical balance of power in preadolescents' mutual friendships

Dyadic friendShip' asymmetry was examined in relation to gender, friendship quality, and friendship status. Sixty-nine grade five children and their mutual, same-sex, friends participated in a laboratory session comprised ofvarious activities and completed questionnaires to identify mutual friends and evaluate friendship quality. Asymmetry of power was assessed observationally during an origami task. Variations in balance of power were evident in children's friendships. Boys' dyads had significantly greater levels of asymmetry than girls' dyads. Regardless of gender, asymmetry was associated with lower friendship quality, particularly as indexed by validation and caring and conflict resolution. Asymmetry was unrelated to differences in friendship status. Furthermore, relative individual power within the friendship was not related to individual perceptions offriendship quality. The implications ofthese findings in the theoretical and empirical literature were considered and suggestions for future research were made.

What Matters? : the full-time graduate students' perceptions of teacher effectiveness

The purpose of this qualitative study was to explore the full-time graduate students' perceptions of teacher effectiveness at the graduate school level, to identify how graduate students perceive effective and ineffective teachers, and specifically to discover the main dimensions of teacher effectiveness that graduate students perceive as most significant. This topic was investigated because, although the teacher has been deemed as a crucial component in the teaching process, there is no common agreement on the definition and measure of teacher effectiveness. Graduate students' perceptions of teacher effectiveness have not been given much attention. The research design was based on a ground theory approach. It utilized qualitative data through interviews, field notes, andjournals. The findings ofthis study revealed that teacher effectiveness is markedly influential to graduate students. There is no universally consented definition or measure of teacher effectiveness due to the multidimensionality of teaching and learning. Nevertheless, several major dimensions ofteacher effectiveness were discovered and highlighted in this study. Such dimensions include good command of subject matter, presentation skills, challenging and motivating students, rapport with students, learning environment, course demands, as well as assessment and feedback. It was hoped that the study would move towards developing a theory that contributes to the knowledge base of graduate students' perceptions of teacher effectiveness. It was anticipated that the results would provide first-hand information for the instructor to improve teaching; for the administrator to promote the effective educational experiences and student achievements. It was intended that the findings would lay a theoretical and empirical groundwork for future research.

Conduct Disorder: A Handbook for Elementary School Educators

This research project examined the behavioural, social, and emotional issues affecting children and youth with conduct disorder. Based on the literature review, the deconstruction of theoretical and empirical studies, and findings from the needs assessment, Conduct Disorder: A Handbook for Elementary School Educators was created. This handbook was developed based on the evidence that conduct problems can most effectively be improved when multiple systems are included in the prevention and intervention of the disorder. Educators, related service providers, and the child all play an important role in designing and implementing effective interventions. Therefore, it is imperative to provide educators with the information necessary to begin this emerging collaborative process. The handbook was created as a tool for educators intending to enhance their knowledge when working with students with conduct disorder. A Needs Assessment was conducted to determine what educators wanted the handbook to contain to assist them in working with students displaying conduct problems. The educators evaluated the handbook, providing constructive feedback and confirming the potential value and practicality of this handbook for elementary school educators. The educators reported an increase in their understanding of conduct disorder, as well as a heightened awareness of the causal factors that contribute to the disorder. The list of community resources and agencies was thought to be a good starting point for educators looking for supplementary aids. The educators indicated that the handbook is a good reference tool to use when teaching students with conduct problems. The educators concluded with the hope that this handbook will be shared with others.

Working Memory in the Junior/Intermediate Classroom

This research project explored the connection between working memory and children’s learning. The project created a resource titled Working Memory Strategies for the Junior/ Intermediate Educator: A Handbook based on a literature review, the deconstruction of theoretical and empirical studies, teacher resources, and findings from a needs assessment completed by teachers that together show there is insufficient support for teachers working with students who have deficits in working memory along with other common classroom learning disabilities. As learning disabilities become more common in the classroom that increasingly affect working memory in a majority of cases, teachers must be prepared not only to address specific symptoms of the conditions, but also to help students learn how to navigate and become aware of their working memory ability. The handbook thus was developed as a useful resource for teachers looking to expand their knowledge about how learning occurs. A needs assessment completed by junior and intermediate division teachers in Ontario helped determine what educators found most important for inclusion in the handbook, and the same teachers were offered the opportunity to review the completed handbook. Teacher participants provided constructive feedback and indicated that the handbook would be a valuable resource for them and their colleagues when working with students who have working memory issues. It was suggested that the handbook would be useful when creating students’ Individual Education Plans and that the assessment checklist included in the handbook would be an excellent resource for teachers collecting data regarding students’ working memory and ability to learn.