Calculation of nondifferential properties for atomic ground states /

A new method for sampling the exact (within the nodal error) ground state distribution and nondiflPerential properties of multielectron systems is developed and applied to firstrow atoms. Calculated properties are the distribution moments and the electronic density at the nucleus (the 6 operator). For this purpose, new simple trial functions are developed and optimized. First, using Hydrogen as a test case, we demonstrate the accuracy of our algorithm and its sensitivity to error in the trial function. Applications to first row atoms are then described. We obtain results which are more satisfactory than the ones obtained previously using Monte Carlo methods, despite the relative crudeness of our trial functions. Also, a comparison is made with results of highly accurate post-Hartree Fock calculations, thereby illuminating the nodal error in our estimates. Taking into account the CPU time spent, our results, particularly for the 8 operator, have a relatively large variance. Several ways of improving the eflSciency together with some extensions of the algorithm are suggested.

Modifications to the Suzuki reaction and mechanistic insights on the NBS mediated cleavage of benzylidene acetals /

One of the most challenging tasks for a synthetic organic chemist today, is the development of chemo, regio, and stereoselective methodologies toward the total synthesis of macromolecules. r . The objective of my thesis was to develop methodologies towards this end. The first part of my project was to develop highly functionalized chirons from D-glucose, a cheap, chiral starting material, to be utilized in this capacity. The second part of the project dealt with modifying the carbon-carbon bond forming Suzuki reaction, which is utilized quite often as a means of combining molecular sub units in total synthesis applications. As previously stated the first area of the project was to develop high value chirons from D-glucose, but the mechanism of their formation was also investigated. The free radical initiated oxidative fragmentation of benzylidene acetals was investigated through the use of several test-case substrates in order to unravel the possible mechanistic pathways. This was performed by reacting the different acetals with N-bromosuccinimide and benzoyl peroxide in chlorobenzene at 70^C in all cases. Of the three mechanistic pathways discussed in the literature, it was determined, from the various reaction products obtained, that the fragmentation of the initial benzylic radical does not occur spontaneously but rather, oxidation proceeds to give the benzyl bromide, which then fragments via a polar pathway. It was also discovered that the regioselectivity of the fragmentation step could be altered through incorporation of an allylic system into the benzylidene acetal. This allows for the acquisition of a new set of densely functionalized. chiral, valuable synthetic intermediates in only a few steps and in high yields from a-Dglucose. The second part of the project was the utilization of the phosphonium salt room temperature ionic liquid tetradecyltrihexylphosphonium chloride (THPC) as an efficient reusable medium for the palladium catalyzed Suzuki cross-coupling reaction of aryl halides, including aryl chlorides, under mild conditions. The cross-coupling reactions were found to proceed in THPC containing small amounts of water and toluene using potassium phosphate and 1% Pd2(dba)3. Variously substituted iodobenzenes, including electron rich derivatives, reacted efficiently in THPC with a variety of arylboronic acids and afforded complete conversion within 1 hour at 50 ^C. The corresponding aryl bromides also reacted under these conditions with the addition of a catalytic amount of triphenylphosphine that allowed for complete conversion and high isolated yields. The reactions involving aryl chlorides were considerably slower, although the addition of triphenylphosphine and heating at 70 ^C allowed high conversion of electron deficient derivatives. Addition of water and hexane to the reaction products results in a triphasic system in which the top hexane phase contained the biaryl products, the palladium catalyst remained fully dissolved in the central THPC layer, while the inorganic salts were extracted into the lower aqueous phase. The catalyst was then recycled by removing the top and bottom layers and adding the reagents to the ionic liquid which was heated again at 50 ^C; resulting in complete turnover of iodobenzene. Repetition of this procedure gave the biphenyl product in 82-97% yield (repeated five times) for both the initial and recycled reaction sequences.

The generation effect and word learning: a test of the effect of the language experience approach versus the text approach in the acquisition of new reading vocabulary

A class of twenty-two grade one children was tested to determine their reading levels using the Stanford Diagnostic Reading Achievement Test. Based on these results and teacher input the students were paired according to reading ability. The students ages ranged from six years four months to seven years four months at the commencement of the study. Eleven children were assigned to the language experience group and their partners became the text group. Each member of the language experience group generated a list of eight to be learned words. The treatment consisted of exposing the student to a given word three times per session for ten sessions, over a period of five days. The dependent variables consisted of word identification speed, word identification accuracy, and word recognition accuracy. Each member of the text group followed the same procedure using his/her partner's list of words. Upon completion of this training, the entire process was repeated with members of the text group from the first part becoming members of the language experience group and vice versa. The results suggest that generally speaking language experience words are identified faster than text words but that there is no difference in the rate at which these words are learned. Language experience words may be identified faster because the auditory-semantic information is more readily available in them than in text words. The rate of learning in both types of words, however, may be dictated by the orthography of the to be learned word.

Forsaking all others: towards a new model of nationalism utilizing the case study of former Yugoslavia

Many people would like to believe that nationalism is a thing of the past, a dinosaur belonging to some bygone, uncivilized era. Such a belief is not borne out by recent history, however. Nationalism occupies the political forum with as much force as ever. Yet, in many ways, it remains a mystery to us. The purpose of this study is to explore individual motivations involved in the rise of nationalism, in addition to the role of structural factors. The linkage employed in this exploration is the psychosocial phenomenon of self-identity, including emotions and self-esteem. We demonstrate how individual, socially-constructed self-identity accounts for why some people embrace nationalism while others eschew it. The methodology employed was theoretical and historical analyses of secondary sources and indepth interviews with subjects who had some connection with former Yugoslavia, the country utilized to test the new model. Our analyses yielded the result that current conceptualizations of nationalism from an exclusively macro or micro perspective are unsatisfactory; we require a more comprehensive approach wherein the two perspectives are integrated. Such an integration necessitates a bridge: hence, our new model, which rests on the psychosocial premise, offers a more useful conceptual tool for the understanding of nationalism. We conclude that nationalism is first and foremost a matter relating to individual social self-identity which takes place within a particular context where oppositional forces emerge from structural factors and our membership in a particular group becomes paramount.

Posttraumatic stress disorder symptoms might be destroying your intimacy : a test of mediational models in a community sample of couples

The present research focused on the pathways through which the symptoms of posttraumatic stress disorder (PTSD) may negatively impact intimacy. Previous research has confirmed a link between self-reported PTSD symptoms and intimacy; however, a thorough examination of mediating paths, partner effects, and secondary traumatization has not yet been realized. With a sample of 297 heterosexual couples, intraindividual and dyadic models were developed to explain the relationships between PTSD symptoms and intimacy in the context of interdependence theory, attachment theory, and models of selfpreservation (e.g., fight-or-flight). The current study replicated the findings of others and has supported a process in which affective (alexithymia, negative affect, positive affect) and communication (demand-withdraw behaviour, self-concealment, and constructive communication) pathways mediate the intraindividual and dyadic relationships between PTSD symptoms and intimacy. Moreover, it also found that the PTSD symptoms of each partner were significantly related; however, this was only the case for those dyads in which the partners had disclosed most everything about their traumatic experiences. As such, secondary traumatization was supported. Finally, although the overall pattern of results suggest a total negative effect of PTSD symptoms on intimacy, a sex difference was evident such that the direct effect of the woman's PTSD symptoms were positively associated with both her and her partner's intimacy. I t is possible that the Tend-andBefriend model of threat response, wherein women are said to foster social bonds in the face of distress, may account for this sex difference. Overall, however, it is clear that PTSD symptoms were negatively associated with relationship quality and attention to this impact in the development of diagnostic criteria and treatment protocols is necessary.