The near ultraviolet absorption spectrum of phosgene /

The near ultraviolet absorption of phosgene has been assigned to a * 1 1 ~.--n, A;-- Al electronic transition from vapour phase spectra recorded under conditions of high resolution and low_t~mperature. Progressions in Vi, v2' V3' V4 and V4 ha\1e been identified in the spectrum and have been analyzed in terms of vibronic transitions between a planar ground and a nonplanar excited state. A ba~rier height of 3170 cm~l:and a nona planar equilibrium angle of 32.5 were calculated for the upper state from a fit of the energy levels of a Lorentzian-guadratic potential func- ~ion to the observed levels of V 4 . ' ~he false ori- 3in, 41 0 , of the spectrum has been assigned to the band at 33,631 cm -1 . An oscillator strength of -3 1 . 1 f = 1. a x 10 has been obtained for the A - A 2 1 transition.

Spectroscopic and theoretical considerations of cyclopropenone

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 D53 2007

Synechococcus sp. PCC 7002 CpcB lyase null mutations alter phycocyanin chromophore function and, consequently, affect the redistribution of excitation energy via the light state transition /

Phycobilisomes are the major light harvesting complexes for cyanobacteria and phycocyanin is the primary phycobiliprotein of the phycobilisome rod. The phycocyanobilin lyases responsible for chromophorylating the phycocyanin p subunit (CpcB) have been recently identified in the cyanobacterium Synechococcus sp. PCC 7002. Surprisingly, mutants missing the CpcB lyases were nevertheless capable of producing pigmented phycocyanin. 10K absorbance measurements revealed that the energy states of the p phycocyanin chromophores were only subtly shifted; however, 77K steady state fluorescence emission spectroscopy showed excitation energy transfer involving the targeted chromophores to be highly disrupted. Such evidence suggests that phycobilin orientation within the binding domain is specifically modified. We hypothesized that alternate, less specific lyases are able to act on the p binding sites. A phycocyanin linker-polypeptide deficient mutant was similarly characterized. The light state transition, a short term adaptation of the photosynthetic light harvesting apparatus resulting in the redistribution of excitation energy among the photo systems, was shown to be dominated by the reallocation of phycocyanin-absorbed excitation energy. Treatment with a high M phosphate buffer effectively prevented the redistribution of both chlorophyll a- and phycobilisome- absorbed excitation energy, suggesting that the two effects are not strictly independent. The mutant strains required a larger redistribution of excitation energy between light states, perhaps to compensate for their loss in phycobilisome antenna function.

The mechanism of the regulation of energy distribution between photosystems 1 and 2 in the cyanobacterium Synechococcus sp. strain PCC 7002 /

Cyanobacteria are able to regulate the distribution of absorbed light energy between photo systems 1 and 2 in response to light conditions. The mechanism of this regulation (the state transition) was investigated in the marine cyanobacterium Synechococcus sp. strain PCC 7002. Three cell types were used: the wild type, psaL mutant (deletion of a photo system 1 subunit thought to be involved in photo system 1 trimerization) and the apcD mutant (a deletion of a phycobilisome subunit thought to be responsible for energy transfer to photo system 1). Evidence from 77K fluorescence emission spectroscopy, room temperature fluorescence and absorption cross-section measurements were used to determine a model of energy distribution from the phycobilisome and chlorophyll antennas in state 1 and state 2. The data confirm that in state 1 the phycobilisome is primarily attached to PS2. In state 2, a portion of the phycobilisome absorbed light energy is redistributed to photo system 1. This energy is directly transferred to photo system 1 by one of the phycobilisome terminal emitters, the product of the apcD gene, rather than via the photo system 2 chlorophyll antenna by spillover (energy transfer between the photo system 2 and photo system 1 chlorophyll antenna). The data also show that energy absorbed by the photo system 2 chlorophyll antenna is redistributed to photo system 1 in state 2. This could occur in one of two ways; by spillover or in a way analogous to higher plants where a segment of the chlorophyll antenna is dissociated from photo system 2 and becomes part of the photo system 1 antenna. The presence of energy transfer between neighbouring photo system 2 antennae was determined at both the phycobilisome and chlorophyll level, in states 1 and 2. Increases in antenna absorption cross-section with increasing reaction center closure showed that there is energy transfer (connectivity) between photosystem 2 antennas. No significant difference was shown in the amount of connectivity under these four conditions.

Electronic and magnetic properties of LaV1-xO3 /

A series of LaVi^xOs compounds (x=0.00, 0.02, 0.04, 0.06, 0.08) were prepeired using the standard solid reaction. The samples were chareicterized by X-ray diffraction (XRD), fourprobe resistivity, smd magnetic susceptibility studies. Powder X-ray diffraction analysis indicated the formation of a single-phase sample with a orthorhombic structure which was first found in GdFeOs (space group Pnma) . The Unit Cell program was used for calculating lattice peirameters from XFID data. The XRD spectnim could be indexed on a cubic lattice with Og = 2ap ~ (7.8578 to 7.9414 A). The lattice parameter was observed to increase as the Vanadium vacancy increased. Four-probe resistivity measurements exhibited semiconductor behavior for all sajnples from room temperature down to 19K. The resistivity of samples increased with increasing Vanadium vacancy. The resistivity of samples demonstrated activated conduction with an activation energy of approximately 0.2 eV. The activation energy increased with increasing lattice parameter. Field cool magnetic susceptibility measurements were performed with field of 500 G from 300 K to 5 K. These measurements indicated the presence of an antiferromagnetic transition at about 140 K. The data was fitted above Neel temperature to Ciurie-Weiss law yielding a negative parameignetic Curie temperature. This implies that antiferromagnetic ordering is present.

Distribution of excitation energy in photosynthesis: a study of heat loss, photo chemical activity and fluorescence emission in intact calls of cyanobacterium.

Photosynthetic state transitions were investigated in the cyanobacterium Synechococcus sp. PCC 6301 by studying fluorescence emission, heat loss, and PS I activity in intact cells brought to state 1 and state 2. 77K fluorescence emission spectra were modelled with a sum of 6 components corresponding to PBS, PS II, and PS I emissions. The modelled data showed a large decrease in PS II fluorescence accompanied with a small increase in the PS I fluorescence upon transition to state 2 for excitation wavelengths absorbed by both PBS and ChI ll.. The fluorescence changes seen with ChI .a. excitations do not support the predictions of the mobile PBS model of state transition in PBS-containing organisms. Measurements of heat loss from intact cells in the two states were similar for both ChI it. and PBS excitations over three orders of magnitude of laser flash intensity. This suggests that the PBS does not become decoupled from PS II in state 2 as proposed by the PBS detachment model of state transition in PBS-containing organisms. PS I activity measurements done on intact cells showed no difference in the two states, in contrast with the predictions of all of the existing models of state transitions. Based on these results a model for state transition In PBScontaining organisms is proposed, with a PS II photoprotectory function.

Large amplitude motions in the S1 state of formic acid /

A detailed theoretical investigation of the large amplitude motions in the S, excited electronic state of formic acid (HCOOH) was done. This study focussed on the the S, «- So electronic band system of formic acid (HCOOH). The torsion and wagging large amplitude motions of the S, were considered in detail. The potential surfaces were simulated using RHF/UHF ab-initio calculations for the two electronic states. The energy levels were evaluated by the variational method using free rotor basis functions for the torsional coordinates and harmonic oscillator basis functions for the wagging coordinates. The simulated spectrum was compared to the slit-jet-cooled fluorescence excitation spectrum allowing for the assignment of several vibronic bands. A rotational analysis of certain bands predicted that the individual bands are a mixture of rotational a, b and c-type components.The electronically allowed transition results in the c-type or Franck-Condon band and the electronically forbidden, but vibronically allowed transition creates the a/b-type or Herzberg-Teller components. The inversion splitting between these two band types differs for each band. The analysis was able to predict the ratio of the a, b and c-type components of each band.

Preparing students for the transition from college to work /

The purpose of this study was to examine the perceived preparedness of college students for the transition from college to full-time employment. The study was concerned with the interest and rationale behind developing a required Exit Course for college students in order to improve the college to work transition. As well, possible content of an Exit Course was evaluated. The importance of addressing college to work transitions is highlighted by two phenomena. First, there are specific employability skills that employers in Canada are seeking in newly hired employees. Second, the provincial government in Ontario is determining college funding based on graduate employment statistics which are measured by graduate satisfaction, graduate employment, and employer satisfaction. The research concentrated on the following stakeholders involved in the transition from college to work: (a) current students, (b) recent graduates, (c) support staff who assist students in college to work transition (Career Educators), and (d) employers. Through qualitative research, including focus groups and interviews, these stakeholder groups participated in the research to determine if the Exit Course was a viable solution to facilitate the transition from college to work. Focus groups were conducted with current students, while one-on-one, semi-structured interviews were conducted with recent graduates, Career Educators, and employers. Common themes elicited from the participants included the following: (a) although students were perceived by the participants of this study to be technically prepared for employment, they were perceived to have weak job search skills and unrealistic expectations of the world of work unless they had received the benefits of a Co-operative Education experience; (b) an Exit Course was seen as a viable solution to the issues involved in college to work transition; (c) an Exit Course should be comprised of skills necessary to obtain and succeed in a job and the course should be taught by individuals with extensive qualifications in this area; and (d) there is a need to develop college and business partnerships to ensure that students are connected to employers. Educators within post secondary institutions, specifically colleges, can benefit from the information provided within this study to gain a better understanding of the perceived level of preparedness of students for the transition from college to work. Suggestions with regard to how to improve this transition were made, with specific reference to the addition of an Exit Course as one possible solution.

An after-school literacy program : investigating the experiences of students with literacy difficulties, their volunteer tutors, and the tutors' transition into the teaching profession

This research responds to a pervasive call for our educational institutions to provide students with literacy skills, and teachers with the instructional supports necessary to facilitate this skill acquisition. Questions were posed to gain information concerning the efficacy ofteaching literacy strategies to students with learning difficulties, the impact of this training on their volunteer tutors, and the influence of this experience on these tutors' ensuing instructional practice as teacher candidates in a preservice education program. Study #1 compared a nontreatment group of students with literacy difficulties who participated in the program and found that program participants were superior at reading letter patterns and at comprehending the elements of story grammar. Concurrently, the second study explored the experiences of 19 volunteer tutors and uncovered that they acquired instructional skills as they established a knowledge base in teaching reading and writing, and they affirmed personal goals to become future teachers. Study #3 tracked 6 volunteer tutors into their pre-service year and identified their constructions, and beliefs about literacy instruction. These teacher candidates discussed how they had intended to teach reading and writing strategies based on their position that effective teaching ofthese skills in the primary grades is integral to academic success. The teacher candidates emphasized the need to build rapport with students, and the need to exercise flexibility in lesson plan delivery while including activities to meet emotional and developmental requirements of students. The teacher candidates entered their pre-service education with an initial cognition set based on the limited teaching context of tutoring. This foundational ii perception represented their prior knowledge of literacy instruction, a perception that appeared untenable once they were immersed in a regular instructional setting. This disparity provoked some of the teacher candidates to denounce their teacher mentors for not consistently employing literacy strategies and individualized instruction. This critical perspective could have been a demonstration of cognitive dissonance. In the end, when the teacher candidates began to look toward the future and how they would manage the demands of an inclusive classroom, they recognized the differences in the contexts. With an appreciation for the need for balance between prior and present knowledge, the teacher candidates remained committed to implementing their tutoring strategies in future teaching positions. This document highlights the need for teacher candidates with instructional experience prior to teacher education, to engage in cognitive negotiations to assimilate newly acquired pedagogies into existing pedagogies.

Transition into the teaching profession: induction and mentoring issues surrounding secondary music teachers /

The purpose of this study was to investigate the issues surrounding the transition into the teaching profession by specifically focusing on teacher induction and mentoring issues while explicitly addressing matters of concern by secondary music teachers in a large suburban school board in southern Ontario. Participants included beginning teachers with fewer than 5 years of teaching, mid career teachers with between 6 and 15 years of instruction, and experienced teachers with more than 16 years of practice. The ' processes of mentoring and inducting new teachers within the board were examined, along with their relationships between proteges, mentors, and administrators. Further, internal and external programs specifically designed and implemented for newer music teachers were scrutinized and discussed. An analysis of key documents and literature on the subject was performed, and data were collected through 16 personal interviews. The findings suggest that although the necessity of mentoring and induction processes has begun to be recognized, there exists a fundamental relationship between mentoring and induction and the effect of the professional attachments to mentoring; the institutional and administrative supports that are enabled; and essential processes and practices between mentors and proteges. Together these three arms combine to support successfiil induction and mentoring initiatives that will help ease the transition into teaching.

Diffusion Monte Carlo study of electronic properties for H and Be atoms /

We examined three different algorithms used in diffusion Monte Carlo (DMC) to study their precisions and accuracies in predicting properties of isolated atoms, which are H atom ground state, Be atom ground state and H atom first excited state. All three algorithms — basic DMC, minimal stochastic reconfiguration DMC, and pure DMC, each with future-walking, are successfully impletmented in ground state energy and simple moments calculations with satisfactory results. Pure diffusion Monte Carlo with future-walking algorithm is proven to be the simplest approach with the least variance. Polarizabilities for Be atom ground state and H atom first excited state are not satisfactorily estimated in the infinitesimal differentiation approach. Likewise, an approach using the finite field approximation with an unperturbed wavefunction for the latter system also fails. However, accurate estimations for the a-polarizabilities are obtained by using wavefunctions that come from the time-independent perturbation theory. This suggests the flaw in our approach to polarizability estimation for these difficult cases rests with our having assumed the trial function is unaffected by infinitesimal perturbations in the Hamiltonian.

Displaced women professionals: an exploration of perceived learning processes during workplace transition /

This study focused on obtaining a deeper understanding of the perceived learning of female professionals during workplace transition. The women's lived experiences were explored through a feminist interpretive lens (Bloom, 1998). The study also drew upon concepts from adult learning such as barriers and facilitating factors to learning, resistance, transformative learning, and multiple ways of knowing. Five women participated in a 1 -hour interview and a focus group activity. The findings are presented under the 2 broad themes of perceived learning and factors affecting learning. The most common theme of perceived learning was participants' experience of increased self-knowledge. Additionally, while learning was thought of as a struggle, it provided either an opportunity for a reexamination of goals or a reexamination of self. Reflection by participants seemed to follow two orientations and other types of perceived learning included experiential, formal, and informal learning. In the broad theme of factors affecting learning, contradictions and conflict emerged through the examination of participants' multiple subjectivities, and within their naming of many factors as both facilitating factors and barriers to learning. The factors affecting learning themes included personal relationships, professional communities, selfesteem, attitude and emotion, the gendered experience of transition, time, and finances. The final theme explored participants' view of work and their orientations to the future. A proposed model of learning during workplace transition is presented (Figure 1 ) and the findings discussed within this proposed model's framework. Additional developmental theories of women (Josselson, 1987; Levinson & Levinson, 1996), communities of practice theories (Wenger, 1998), and career resilience theories (Pulley, 1995) are discussed within the context of the proposed model. Implications to practice for career counsellors, people going through workplace transition, human resource managers and career coaches were explored. Additionally implications to theory and future areas of research are also discussed.

Optical properties of organic superconductor K-(BETS)2FeBr4 /

K-(BETS)2FeBr4 is a quasi-2D charge transfer organic metal with interesting electronic and magnetic properties. It undergoes a transition to an antiferromagnetic (AF) state at ambient pressure at the Neel temperature (T^^) = 2.5 K, as well as to a superconducting (SC) state at 1.1 K [1]. The temperature dependence of the electrical resistivity shows a small decrease at T;v indicating the resistivity drops as a result of the onset of the ordering of Fe'*''" spins. A sharp drop in the resistivity at 1.1 K is due to its superconducting transition. The temperature dependence of the susceptibility indicates an antiferromagnetic spin structure with the easy axis parallel to the a-axis. The specific heat at zero-field shows a large peak at about 2.4 K, which corresponds to the antiferromagnetic transition temperature (Tat) and no anomaly is observed around the superconducting transition temperature (1.1 K) demonstrating that the magnetically ordered state is not destroyed by the appearance of another phase transition (the superconducting transition) in the 7r-electron layers [1], [2]. This work presents an investigation of how the low frequency electromagnetic response is affected by the antiferromagnetic and superconducting states, as well as the onset of strong correlation. The location of the easy axis of three samples was determined and polarized thermal reflectance measurements of these «-(BETS)2FeBr4 samples oriented with their vertical axis along the a- and c axes were then carried out using a *He refrigerator cryostat and a Martin-Puplett type polarizing interferometer at various temperatures (T = 0.5 K, 1.4 K. 1.9 K, 2.8 K) above and below the superconducting state and/or antiferromagnetic state. Comparison of the SC state to the normal state along the o- and c-axes indicates a rising thermal reflectance at low frequencies (below 10 cm"' ) which may be a manifestation of the superconducting energy gap. A dip-Hke feature is detected at low frequencies (below 15 cm"') in the thermal reflectance plots which probe the antiferromagnetic state along the two axes, and may be due to the opening of a gap in the excitation spectrum as a result of the antiferromagnetism. In another set of experiments, thermal reflectance measurements carried out along the a- and c-axes at higher temperatures (10 K-80 K) show that the reflectivity decreases with increasing temperature to 60 K (the coherence temperature) above which it increases again. Comparison of the thermal reflectance plots along the a- and c-axes at higher temperatures reveals an anisotropy between these two axes. The Hagen-Rubens thermal reflectance plots corresponding to an average over the ac-plane were calculated using experimental hterature resistivity values. Comparison of the Hagen-Rubens plots with the experimental thermal reflectance along the a- and c-axes indicates that both exhibit the general trend of a decrease in thermal reflectance with increasing frequency, however the calculated Hagen-Rubens thermal reflectance at different temperatures is much lower than the experimental curves.

An examination of learning resulting from a transition from a directed to a self-directed work environment

~ This study focuses on the process of self-directed learning that individuals go through as they adapt to new work situations. This is a study of how one critical incident, specifically the transition from a traditional office structure to a home office structure, affected employees and what their learning process was as they adapted to the new environment. This study has 3 educational foundations: adult learning, self-directed learning, and the social context from which the learning will occur. Six women and 2 men were interviewed approximately 1 year following the transition. Analysis of the data revealed 5 themes of: impacts of the self-directed environment on participants' personal lives, their roles, skill set, productivity, and the physical environment; support offered by the organization, family, and office administration; personal development, specific learning needs, and personal skills; boundaries as they relate to family and work; and skill set and orientation requirements of new home office employees. The findings revealed the learning processes of the 8 participants. The learning processes of these participants were discussed within a theoretical framework of the learners, their immediate surroundings, and the larger social environment. The results indicated that the transition from a directed work environment to a self directed work environment is a complex, interrelated process. An element found throughout the theoretical framework is that of control. A second critical element is the need for participants to have a clearly defined work role and an opportunity to engage in discussion with peers and the community. Further findings reinforced the importance of climate and found that the physical environment is a key factor in a successful selfdirected work environment. The findings of this study revealed that no one factor makes an individual function successfully in a self-directed work environment, but that it is a complex interplay among the leamer, their immediate surroundings, and the social environment that will have the greatest impact on success. Recommendations are made which can be used to guide organizational leaders in facilitating employees' transition from a directed to a self-directed work environment. Additionally, recommendations are made for further research in the area of self-directed work environments.

Anharmonic Helmholtz free energy to O(lambdaâ ´) in the non- leading term approximation /|nby Leslie Wilk. -- 260 St. Catharines, Ont. : [s. n.],

Expressions for the anharmonic Helmholtz free energy contributions up to o( f ) ,valid for all temperatures, have been obtained using perturbation theory for a c r ystal in which every atom is on a site of inversion symmetry. Numerical calculations have been carried out in the high temperature limit and in the non-leading term approximation for a monatomic facecentred cubic crystal with nearest neighbour c entralforce interactions. The numbers obtained were seen to vary by a s much as 47% from thos e obtai.ned in the leading term approximati.on,indicating that the latter approximati on is not in general very good. The convergence to oct) of the perturbation series in the high temperature limit appears satisfactory.