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.

Set and Spike

Brock Men's Volleyball makes a play in this 1978 match.

Rotation-electronic interaction in the 3p-complex Rydberg state of water

An energy theory is formulated for the rotational energy levels in a p-complex Rydberg state of an asymmetric top molecule of symmetry C2v. The effective Hamiltonian used consists of the usual rigid rotor Hamiltonian augmented with terms representing electronic spin and orbital angular momentum effects. Criteria for assigning symmetry species to the rotational energy levels, following Houganfs scheme that uses the full molecular group,are established and given in the form of a table. This is particularly suitable when eigenvectors are calculated on a digital computer. Also, an intensity theory for transitions to the Rydberg p-complex singlet states is presented and selection rules in terms of symmetry species of energy states are established. Finally, applications to HpO and DpO are given.

Set-up and evaluation of a mid-infrared reflectometer and investigation of the optical properties of doped tin telluride

A system comprised of a Bomem interferometer and a LT3-110 Heli-Tran cryostat was set up to measure the reflectance of materials in the mid-infrared spectral region. Several tests were conducted to ensure the consistency and reliability of the system. Silicon and Chromium, two materials with well known optical properties were measured to test the accuracy of the system, and the results were found to be in good agreement with the literature. Reflectance measurements on pure SnTe and several Pb and Mn-doped alloys were carried out. These materials were chosen because they exhibit a strong plasma edge in the mid infrared region. The optical conductivity and several related optical parameters were calculated from the measured reflectance. Very low temperature measurements were carried out in the far-infrared on Sn9SMn2Te, and the results are indicative of a spin glass phase at 0.8 K. Resistivity measurements were made at room temperature. The resistivity values were found, as expected, to decrease with increasing carrier concentration and to increase with increasing manganese concentration.

Transmission measurements using a new far-infrared set-up

A system comprised of a Martin-Puplett type polarizing interferometer and a Helium-3 cryostat was developed to study the transmission of materials in the very-far-infrared region of the spectrum. This region is of significant interest due to the low-energy excitations which many materials exhibit. The experimental transmission spectrum contains information concerning the optical properties of the material. The set-up of this system is described in detail along with the adaptations and improvements which have been made to the system to ensure the best results. Transmission experiments carried out with this new set-up for two different varieties of materials: superconducting thin films of lead and biological proteins, are discussed. Several thin films of lead deposited on fused silica quartz substrates were studied. From the ratio of the transmission in the superconducting state to that in the normal state the superconducting energy gap was determined to be approximately 25 cm-1 which corresponds to 2~/kBTc rv 5 in agreement with literature data. Furthermore, in agreement with theoretical predictions, the maximum in the transmission ratio was observed to increase as the film thickness was increased. These results provide verification of the system's ability to accurately measure the optical properties of thin low-Tc superconducting films. Transmission measurements were carried out on double deionized water, and a variety of different concentrations by weight of the globular protein, Bovine Serum Albumin, in the sol, gel and crystalline forms. The results of the water study agree well with literature values and thus further illustrate the reproducibility of the system. The results of the protein experiments, although preliminary, indicate that as the concentration increases the samples become more transparent. Some weak structure in the frequency dependent absorption coefficient, which is more prominent in crystalline samples, may be due to low frequency vibrations of the protein molecules.

Cognitive set, absorption, and achievement as moderators of the perceptual closure effect in picture priming /

The present study examined individual differences in Absorption and fantasy, as well as in Achiievement and achievement striving as possible moderators of the perceptual closure effect found by Snodgrass and Feenan (1990). The study also examined whether different instructions (experiential versus instrumental) interact with the personality variables to moderate the relationship between priming and subsequent performance on a picture completion task. 1 28 participants completed two sessions, one to fill out the MPQ and NEO personality inventories and the other to complete the experimental task. The experimental task consisted of a priming phase and a test phase, with pictures presented on a computer screen for both phases. Participants were shown 30 pictures in the priming phase, and then shovm the 30 primed pictures along with 30 new pictures for the test phase. Participants were randomly assigned to receive one of the two different instruction sets for the task. Two measures of performance were calculated, most fragmented measure and threshold. Results of the present study confirm that a five-second exposure time is long enough to produce the perceptual closure effect. The analysis of the two-way interaction effects indicated a significant quadratic interaction of Absorption with priming level on threshold performance. The results were in the opposite direction of predictions. Possible explanations for the Absorption results include lack of optimal conditions, lack of intrinsic motivation and measurement problems. Primary analyses also revealed two significant between-subject effects of fantasy and achievement striving on performance collapsed across priming levels. These results suggest that fantasy has a beneficial effect on performance at test for pictures primed at all levels, whereas achievement striving seems to have an adverse effect on performance at test for pictures primed at all levels. Results of the secondary analyses with a revised threshold performance measure indicated a significant quadratic interaction of Absorption, condition and priming level. In the experiential condition, test performance, based on Absorption scores for pictures primed at level 4, showed a positive slope and performance for pictures primed at levels 1 and 7 based on Absorption showed a negative slope. The reverse effect was found in the instrumental condition. The results suggest that Absorption, in combination with experiential involvement, may affect implicit memory. A second significant result of the secondary analyses was a linear three-way interaction of Achievement, condition and priming level on performance. Results suggest that as Achievement scores increased, test performance improved for less fragmented primed pictures in the instrumental condition and test performance improved for more highly fragmented primes in the experiential condition. Results from the secondary analyses suggest that the revised threshold measure may be more sensitive to individual differences. Results of the exploratory analyses with Openness to Experience, Conscientiousness and agentic positive emotionality (PEM-A) measures indicated no significant effects of any of these personality variables. Results suggest that facets of the scales may be more useful with regard to perceptual research, and that future research should examine narrowly focused personality traits as opposed to broader constructs.

Determining rotational direction of rotation structures using prolate shaped grains within till

Micromorphology is used to analyze a wide range of sediments. Many microstructures have, as yet, not been analyzed. Rotation structures are the least understood of microstructures: their origin and development forms the basis of this thesis. Direction of rotational movement helps understand formative deformational and depositional processes. Twenty-eight rotation structures were analyzed through two methods of data extraction: (a) angle of grain rotation measured from Nikon NIS software, and (b) visual analyses of grain orientation, neighbouring grainstacks, lineations, and obstructions. Data indicates antithetic rotation is promoted by lubrication, accounting for 79% of counter-clockwise rotation structures while 21 % had clockwise rotation. Rotation structures are formed due to velocity gradients in sediment. Subglacial sediments are sheared due to overlying ice mass stresses. The grains in the sediment are differentially deformed. Research suggests rotation structures are formed under ductile conditions under low shear, low water content, and grain numbers inducing grain-to-grain interaction.

Conceptualizing Institutional Capacity Building Through a Learning Process Set in Motion by a Foundation

Employing critical pedagogy and transformative theory as a theoretical framework, I examined a learning process associated with building capacity in community-based organizations (CBOs) through an investigation of the Institutional Capacity Building Program (ICBP) initiated by a Foundation. The study sought to: (a) examine the importance of institutional capacity building for individual and community development; (b) investigate elements of a process associated with a program and characteristics of a learning process for building capacity in CBOs; and (c) analyze the Foundation’s approach to synthesizing, systematizing, and sharing learning. The study used a narrative research design that included 3 one-on-one, hour-long interviews with 2 women having unique vantage points in ICBP: one is a program facilitator working at the Foundation and the other runs a CBO supported by the Foundation. The interviews’ semistructured questions allowed interviewees to share stories regarding their experience with the learning process of ICB and enabled themes to emerge from their day-to-day experience. Through the analysis of this learning process for institutional capacity building, a few lessons can be drawn from the experience of the Foundation.

GA approach for finding Rough Set decision rules based on bireducts

Feature selection plays an important role in knowledge discovery and data mining nowadays. In traditional rough set theory, feature selection using reduct - the minimal discerning set of attributes - is an important area. Nevertheless, the original definition of a reduct is restrictive, so in one of the previous research it was proposed to take into account not only the horizontal reduction of information by feature selection, but also a vertical reduction considering suitable subsets of the original set of objects. Following the work mentioned above, a new approach to generate bireducts using a multi--objective genetic algorithm was proposed. Although the genetic algorithms were used to calculate reduct in some previous works, we did not find any work where genetic algorithms were adopted to calculate bireducts. Compared to the works done before in this area, the proposed method has less randomness in generating bireducts. The genetic algorithm system estimated a quality of each bireduct by values of two objective functions as evolution progresses, so consequently a set of bireducts with optimized values of these objectives was obtained. Different fitness evaluation methods and genetic operators, such as crossover and mutation, were applied and the prediction accuracies were compared. Five datasets were used to test the proposed method and two datasets were used to perform a comparison study. Statistical analysis using the one-way ANOVA test was performed to determine the significant difference between the results. The experiment showed that the proposed method was able to reduce the number of bireducts necessary in order to receive a good prediction accuracy. Also, the influence of different genetic operators and fitness evaluation strategies on the prediction accuracy was analyzed. It was shown that the prediction accuracies of the proposed method are comparable with the best results in machine learning literature, and some of them outperformed it.

List (11 pages, handwritten) of remarks upon the titles as set forth in the abstracts

List (11 pages, handwritten) of remarks upon the titles as set forth in the abstracts, n.d.