An analysis of the methyl rotation dynamics in the So (x' A) and T (a A) states of thioacetaldehyde from Pyrolysis jet spectra /

Jet-cooled, laser-induced phosphorescence excitation spectra (LIP) of thioacetaldehyde CH3CHS, CH3CDS, CD3CHS and CD3CDS have been observed over the region 15800 - 17300 cm"^ in a continuous pyrolysis jet. The vibronic band structure of the singlet-triplet n -* n* transition were attributed to the strong coupling of the methyl torsion and aldehydic hydrogen wagging modes . The vibronic peaks have been assigned in terms of two upper electronic state (T^) vibrations; the methyl torsion mode v^g, and the aldehydic hydrogen wagging mode v^^. The electronic origin O^a^ is unequivocally assigned as follows: CH3CHS (16294.9 cm"'' ), CH3CDS (16360.9 cm"'' ), CD3CHS (16299.7 cm"^ ), and CD3CDS (16367.2 cm"'' ). To obtain structural and dynamical information about the two electronic states, potential surfaces V(e,a) for the 6 (methyl torsion) and a (hydrogen wagging) motions were generated by ab initio quantum mechanical calculations with a 6-3 IG* basis in which the structural parameters were fully relaxed. The kinetic energy coefficients BQ(a,e) , B^(a,G) , and the cross coupling term B^(a,e) , were accurately represented as functions of the two active coordinates, a and 9. The calculations reveal that the molecule adopts an eclipsed conformation for the lower Sq electronic state (a=0°,e=0"') with a barrier height to internal rotation of 541.5 cm"^ which is to be compared to 549.8 cm"^ obtained from the microwave experiment. The conformation of the upper T^ electronic state was found to be staggered (a=24 . 68° ,e=-45. 66° ) . The saddle point in the path traced out by the aldehyde wagging motion was calculated to be 175 cm"^ above the equilibrium configuration. The corresponding maxima in the path taken by methyl torsion was found to be 322 cm'\ The small amplitude normal vibrational modes were also calculated to aid in the assignment of the spectra. Torsional-wagging energy manifolds for the two states were derived from the Hamiltonian H(a,e) which was solved variationally using an extended two dimensional Fourier expansion as a basis set. A torsionalinversion band spectrum was derived from the calculated energy levels and Franck-Condon factors, and was compared with the experimental supersonic-jet spectra. Most of the anomalies which were associated with the interpretation of the observed spectrum could be accounted for by the band profiles derived from ab initio SCF calculations. A model describing the jet spectra was derived by scaling the ab initio potential functions. The global least squares fitting generates a triplet state potential which has a minimum at (a=22.38° ,e=-41.08°) . The flatter potential in the scaled model yielded excellent agreement between the observed and calculated frequency intervals.

Analysis of the late correspondence between our administration and Great Britain & France, with an attempt to show what are the real causes of the failure of the negotiation.

Ten pieces originally published in the Columbian Centinel. A later edition with imprint New York, Printed for E. Sargeant, 1809, contains two additional pieces.

Supplement to the late analysis of the public correspondence between our Cabinet and those of France and G. Britain /

Caption title.

Analysis Of The A11a22 X 11a11 And A 33a22 X 1 electronic transitions in selenocarbonyl difluoride

The absorption spectrum of F2CSe in the 18800-21900 cm-1 region has been recorded at -770 C and 220 C under the conditions of medium resolution. The responsible electronic promotion is TI* + n excitation which leads to 3A2 and lA2 excited states. Progressions in vI', v2', v3" v4' and v4" have been identified in the spectrum and have been analyzed in terms of vibronic transitions between a planar ground state and a nQnplanar excited state. The - 3 - 1 - 1 - 1 origins of the a A2 + X Al and A A2 + X Al systems were assigned to the bands at 19018 cm-l and 19689 cm-l . This has given a singlet-triplet splittl. n g lA2 - 3A2 P f 671 cm -1 The out-of-plane wagging levels were found to be anharmonic. 1 -1 Barrier heights of 2483 cm- and 2923 cm were obtained for the lA2 and 3A2 upper states from a fitting of the energy levels of a Lorentzian-quadratic function to the observed levels in the out-of-plane wagging modes. 1 3 For the A2 and A2 states nonplanar equilibrium angles of 30.10 and 31.40 have been evaluated respectively. i

An analysis of the systemic aspects of rights training for people with intellectual disabilities

Individuals with intellectual disabilities (ID) as a group have been subject to abuse. Individuals with ID need to be made aware of their rights. The 3Rs: Rights, Respect and Responsibility Human Rights Project is promoting rights awareness in individuals with ID, their caregivers and family members. To be effeCtive, abuse prevention must include support from the whole organization and its processes. This research evaluated the impact of the 3Rs initiative on the organization. It focused particularly on descriptions of organizational change perceived by full-time staff and managers in response to the initiation of the 3Rs Project. Behavioural interviews were conducted and a thematic analysis was used to describe changes in the organizational culture and behavioural mechanisms maintaining these changes. Systemic barriers to change were also explored. The results indicate that the Association is effectively implementing and supporting the rights-based philosophy.

An analysis of the relationship between self-efficacy and performance in a continuous gymnastic routine

Research has shown a consistent correlation between efficacy and sport performance (Moritz, et aI., 2000). This relationship has been shown to be dynamic and reciprocal over seasons (e.g., Myers, Payment, et aI., 2004), within games (e.g., Butt, et aI., 2003), and across trials (e.g., Feltz, 1982). The purpose of the present study was to examine selfefficacy and performance simultaneously within one continuous routine. Forty-seven undergraduate students performed a gymnastic sequence while using an efficacy measure. Results indicated that the efficacy-performance relationship was not reciprocal; previous performance was a significant predictor of subsequent performance (p < .01; f3s ranged from .44 to .67). Results further revealed significant differences in efficacy beliefs between groups with high and low levels of performance [F (1,571) = 7.16,p < .01]. Findings suggest that high levels of performance within a continuous physical activity task result in higher performance scores and higher efficacy beliefs.

Nietzsche's children : a physiological analysis of the scholar's task

Throughout Nietzsche's writings we find discussions of the proper relationship of the scholar/scientist to the philosopher, wi th the scholar of ten being presented in a derogatory light. In this thesis, I examine Nietzsche's por t rai t of the scholar through the lens of his physiological or clinical perspective as articulated by Dr. Daniel R. Ahern in his monograph entitled Nietzsche as Cultural Physician. My aim in doing so is to grasp the affirmative, creative aspect of this seemingly destructive polemic against scholars. I begin wi th a detailed discussion of Nietzsche's por t rai t of the scholar in Beyond Good and Evil. This includes an explication of Ahern's position, followed by an application of the diagnostic perspective to Nietzsche's discussion of the objective type, the skeptic, and the critic. I then look at how the characteristics of all three types are present in the Nietzschean 'free spirit.' I also discuss the physiological basis of esotericism in Nietzsche's work, as well as Nietzsche's revaluation of the scholarly vi r tue known as Red/ichkeit (or 'honesty'). I conclude wi th comments on the free spirit's relationship to the future.

Rotational analysis of the 5 1 0 6 1 0 band of formyl chloride

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 C54 L434 1989

Factors Contributing to Reading Performance: An In-Depth Analysis of the “Boy Crisis”

This research used a quantitative study approach to investigate the “boy crisis” in Canada. Boy crisis advocates suggest that boys are being surpassed by girls on reading assessments and promote strategies to assist male students. A feminist framework was used in this study that allowed for an investigation and discussion of the factors that mediate between gender and success at reading comprehension, interpretation, and response to text without ignoring female students. Reading scores and questionnaire data compiled by the Pan-Canadian Assessment Program were used in this research, specifically the PCAP-13 2007 assessment of approximately 30,000 13-year-old students from all Canadian provinces and Yukon Territory (CMEC, 2008). Approximately 20,000 participants wrote the reading assessment, while 30,000 students completed the questionnaire responses. Predictor variables were tested using parametric tests such as independent samples t-test, one-way ANOVA, chi-square analysis, and Pearson r. Findings from this study indicate that although boys scored lower than girls on the PCAP-13 2007 reading assessment, factors were found to influence the reading scores of both male and female students to varying degrees. Socioeconomic status, perceptions of the reading material used in language arts classrooms, reading preference, reading interest, parental involvement, parental encouragement for reading, and self-efficacy were all found to affect the reading performance of boys and girls. Relationships between variables were also found and are discussed in this research. The analysis presented in this study allows parents, educators, and policy makers to begin to critically examine and re-evaluate boy crisis literature and offers suggestions on how to improve reading performance for all students of all socioeconomic backgrounds.

In danger of jammed minds: A deconstructive discourse analysis of the criteria for early onset schizophrenia and imagination in children's literature

The purpose of this research is to expose and complicate those discourses of childhood imagination as demonstrated in the diagnostic criteria for early onset schizophrenia by using an antipsychiatry perspective. This will be done by evaluating those discourses alongside those found in popular children’s literature, specifically, Harry Potter and The Philosopher’s Stone, Bridge to Terabithia, and A Wrinkle in Time. Once uncovered, the underlying power discourses were then exposed. This research will then employ a minor reading as provided by Deleuze and Guattari’s (1987) approach to minor literature to demonstrate the ways in which the child can subvert those dominant discourses. The potential of literature is evaluated for its ability to provide alternative modes of experience and lines of flight for the child subjected to the diagnostic criteria of schizophrenia.