Investigation of molecular polarizabilities and derivatives in halomethanes

The research undertaken was to obtain absolute Raman intensities for the symmetric stretching vibrations of the methyl halides, CH3X with (X=F, CI, Br), by experiment and theory. The intensities were experimentally measured using the Ar+ ion gas laser as excitation source, a Spex 14018 double monochromator and a RCA C-31034 photomultiplier tube as detector. These intensities arise from changes in the derivative of the polarizability (8 a'), with respect to vibration along a normal coordinate (8qi). It was intended that these derivatives obtained with respect to normal coordinates would be converted to derivatives with respect to internal coordinates, for a quantitative comparison with theory. Theoretical numerical polarizability derivatives for the stretching vibrations are obtained using the following procedure. A vibration was simulated in the molecule by increasi.ng and decreasing the respective bond by the amount ±o.oosA for the C-H bonds and ±o.oIA for the C-X (X=F, CI, Br) bond. The derivative was obtained by taking the difference in the polarizability for the equilibrium geometry and the geometry when a particular bond is changed. This difference, when divided by the amount of change in each bond and the number of bonds present results in the derivative of the polarizability with respect to internal coordinate i.e., !1u/!1r. These derivatives were obtained by two methods: I} ab initio molecular orbital calculation and 2} theory of atoms in molecules (AIM) analysis. Due to errors in the experimental setup only a qualitative analysis of the results was undertaken relative to the theory. Theoretically it is predicted that the symmetric carbonhalogen stretch vibrations are more intense than the respective carbon-hydrogen stretch, but only for the methyl chloride and bromide. The carbon fluorine stretch is less intense than the carbon-hydrogen stretch, a fact which is attributed to the small size and high electronegativity of the fluorine atom. The experimental observations are seen to agree qualitatively with the theory results. It is hoped that when the experiment is repeated, a quantitative comparison can be made. The analysis by the theory of atoms in molecules, along with providing polarizabilities and polarizability derivatives, gives additional information outlined below. The theory provides a pictorial description of the main factors contributing to the molecular polarizability and polarizability derivative. These contributions are from the charge transfer and atomic dipole terms i.e., transfer of charge from one atom to another and the reorganization of atomic electronic charge distribution due to presence of an electric field. The linear relationship between polarizability and molecular volume was also observed.

'To do justice and judgement' : the place of passion in public life

Please consult the paper edition of this thesis to read. It is available on the 5th Floor of the Library at Call Number: Z 9999 P65 F47 2003

Agrarian revolution in Central America : a comparison of Nicaragua and Honduras using Jeffery Paige's theory of Agrarian revolution

ABSTRACT In 1979 Nicaragua, under the Sandinistas, experienced a genuine, socialist, full scale, agrarian revolution. This thesis examines whether Jeffery Paige's theory of agrarian revolutions would have been successful in predicting this revolution and ln predicting non-revolution in the neighboring country of Honduras. The thesis begins by setting Paige's theory in the tradition of radical theories of revolution. It then derives four propositions from Paige's theory which suggest the patterns of export crops, land tenure changes and class configurations which are necessary for an agrarian and socialist revolution. These propositions are tested against evidence from the twentieth century histories of economic, social and political change in Nicaragua and Honduras. The thesis concludes that Paige's theory does help to explain the occurrence of agrarian revolution in Nicaragua and non-revolution in Honduras. A fifth proposition derived from Paige's theory proved less useful in explaining the specific areas within Nicaragua that were most receptive to Sandinista revolutionary activity.

An experimental investigation of dechanneling in copper single crystals

This investigation comprises a comparison of experimental and theoretical dechanneling of MeV protons in copper single crystals. Dechanneling results when an ion's transverse energy increases to the value where the ion can undergo small impact parameter collisions with individual atoms. Depth dependent dechanneling rates were determined as functions of lattice temperature, ion beam energy and crystal axis orientation. Ion beam energies were IMeV and 2MeV,temperatures ranged from 35 K to 280 K and the experiment was carried out along both the (lOa) and <110) axes. Experimental data took the form of aligned and random Rutherford backscattered energy spectra. Dechanneling rates were extracted from these spectra using a single scattering theory that took explicit account of the different stopping powers experienced by channeled and dechanneled ions and also included a correction factor to take into account multiple scattering effects along the ion's trajectory. The assumption of statistical equilibrium and small angle scattering of the channeled ions allows a description of dechanneling in terms of the solution of a diffusion like equation which contains a so called diffusion function. The diffusion function is shown to be related to the increase in average transverse energy. Theoretical treatments of increase in average transverse energy due to collisions of projectiles with channel electrons and thermal perturbations in the lattice potential are reviewed. Using the diffusion equation and the electron density in the channel centre as a fitting parameter dechanneling rates are extracted. Excellent agreement between theory and experiment has been demonstrated. Electron densities determined in the fitting procedure appear to be realistic. The surface parameters show themselves to be good indicators of the quality of the crystal.

Examining sport commitment and intentions to participate in intramural sports : application of the Sport Commitment Model and the Theory of Planned Behaviour in a campus recreational sport setting

Fifty-six percent of Canadians, 20 years of age and older, are inactive (Canadian Community Health Survey, 200012001). Research has indicated that one of the most dramatic declines in population physical activity occurs between adolescence and young adulthood (Melina, 2001; Stephens, Jacobs, & White, 1985), a time when individuals this age are entering or attending college or university. Colleges and universities have generally been seen as environments where physical activity and sport can be promoted and accommodated as a result of the available resources and facilities (Archer, Probert, & Gagne, 1987; Suminski, Petosa, Utter, & Zhang, 2002). Intramural sports, one of the most common campus recreational sports options available for post-secondary students, enable students to participate in activities that are suited for different levels of ability and interest (Lewis, Jones, Lamke, & Dunn, 1998). While intramural sports can positively affect the physical activity levels and sport participation rates of post-secondary students, their true value lies in their ability to encourage sport participation after school ends and during the post-school lives of graduates (Forrester, Ross, Geary, & Hall, 2007). This study used the Sport Commitment Model (Scanlan et aI., 1993a) and the Theory of Planned Behaviour (Ajzen, 1991) with post secondary intramural volleyball participants in an effort to examine students' commitment to intramural sport and 1 intentions to participate in intramural sports. More specifically, the research objectives of this study were to: (1.) test the Sport Commitment Model with a sample of postsecondary intramural sport participants(2.) determine the utility of the sixth construct, social support, in explaining the sport commitment of post-secondary intramural sport participants; (3.) determine if there are any significant differences in the six constructs of IV the SCM and sport commitment between: gender, level of competition (competitive A vs. B), and number of different intramural sports played; (4.) determine if there are any significant differences between sport commitment levels and constructs from the Theory of Planned Behaviour (attitudes, subjective norms, perceived behavioural control, and intentions); (5.) determine the relationship between sport commitment and intention to continue participation in intramural volleyball, continue participating in intramurals and continuing participating in sport and physical activity after graduation; and (6.) determine if the level of sport commitment changes the relationship between the constructs from the Theory of Planned Behaviour. Of the 318 surveys distributed, there were 302 partiCipants who completed a usable survey from the sample of post-secondary intramural sport participants. There was a fairly even split of males and females; the average age of the students was twenty-one; 90% were undergraduate students; for approximately 25% of the students, volleyball was the only intramural sport they participated in at Brock and most were part of the volleyball competitive B division. Based on the post-secondary students responses, there are indications of intent to continue participation in sport and physical activity. The participation of the students is predominantly influenced by subjective norms, high sport commitment, and high sport enjoyment. This implies students expect, intend and want to 1 participate in intramurals in the future, they are very dedicated to playing on an intramural team and would be willing to do a lot to keep playing and students want to participate when they perceive their pursuits as enjoyable and fun, and it makes them happy. These are key areas that should be targeted and pursued by sport practitioners.

Toward a grounded theory of trigger events and leadership development in early adulthood

The purpose of this research study was to develop a conceptual model through the use of a grounded theory approach, which explains how trigger events are related to leadership development. Trigger events are experience that cause developmental growth and may result in an increased ability to lead (Luthans and Avolio (2003). In this study, there were two phases of data collection. First participants completed the Washington University Sentence Completion Test (WUSCT), where their respective leadership developmental stage was measured. Second, participants were involved in two in-depth interviews where an understanding was reached as to how various trigger events have impacted their leadership development. From these data, a conceptual model was developed to explain the relationship between trigger events and leadership development. Participants described trigger events as being important developmental periods, during which time they grew as people and became more capable leaders.

Towards automated derivation in the theory of allegories

We provide an algorithm that automatically derives many provable theorems in the equational theory of allegories. This was accomplished by noticing properties of an existing decision algorithm that could be extended to provide a derivation in addition to a decision certificate. We also suggest improvements and corrections to previous research in order to motivate further work on a complete derivation mechanism. The results presented here are significant for those interested in relational theories, since we essentially have a subtheory where automatic proof-generation is possible. This is also relevant to program verification since relations are well-suited to describe the behaviour of computer programs. It is likely that extensions of the theory of allegories are also decidable and possibly suitable for further expansions of the algorithm presented here.

Optimizing Computational Frameworks to Study the Influence of the Protein Environment on the Individual Site Energies of Chromophores in Photosystem II of Photosynthesis

Photosynthesis is a process in which electromagnetic radiation is converted into chemical energy. Photosystems capture photons with chromophores and transfer their energy to reaction centers using chromophores as a medium. In the reaction center, the excitation energy is used to perform chemical reactions. Knowledge of chromophore site energies is crucial to the understanding of excitation energy transfer pathways in photosystems and the ability to compute the site energies in a fast and accurate manner is mandatory for investigating how protein dynamics ef-fect the site energies and ultimately energy pathways with time. In this work we developed two software frameworks designed to optimize the calculations of chro-mophore site energies within a protein environment. The first is for performing quantum mechanical energy optimizations on molecules and the second is for com-puting site energies of chromophores in a fast and accurate manner using the polar-izability embedding method. The two frameworks allow for the fast and accurate calculation of chromophore site energies within proteins, ultimately allowing for the effect of protein dynamics on energy pathways to be studied. We use these frame-works to compute the site energies of the eight chromophores in the reaction center of photosystem II (PSII) using a 1.9 Å resolution x-ray structure of photosystem II. We compare our results to conflicting experimental data obtained from both isolat-ed intact PSII core preparations and the minimal reaction center preparation of PSII, and find our work more supportive of the former.