33 resultados para Concept of angle
em Brock University, Canada
Resumo:
The topic of this thesis is marginaVminority popular music and the question of identity; the term "marginaVminority" specifically refers to members of racial and cultural minorities who are socially and politically marginalized. The thesis argument is that popular music produced by members of cultural and racial minorities establishes cultural identity and resists racist discourse. Three marginaVminority popular music artists and their songs have been chosen for analysis in support of the argument: Gil Scott-Heron's "Gun," Tracy Chapman's "Fast Car" and Robbie Robertson's "Sacrifice." The thesis will draw from two fields of study; popular music and postcolonialism. Within the area of popular music, Theodor Adorno's "Standardization" theory is the focus. Within the area of postcolonialism, this thesis concentrates on two specific topics; 1) Stuart Hall's and Homi Bhabha's overlapping perspectives that identity is a process of cultural signification, and 2) Homi Bhabha's concept of the "Third Space." For Bhabha (1995a), the Third Space defines cultures in the moment of their use, at the moment of their exchange. The idea of identities arising out of cultural struggle suggests that identity is a process as opposed to a fixed center, an enclosed totality. Cultures arise from historical memory and memory has no center. Historical memory is de-centered and thus cultures are also de-centered, they are not enclosed totalities. This is what Bhabha means by "hybridity" of culture - that cultures are not unitary totalities, they are ways of knowing and speaking about a reality that is in constant flux. In this regard, the language of "Otherness" depends on suppressing or marginalizing the productive capacity of culture in the act of enunciation. The Third Space represents a strategy of enunciation that disrupts, interrupts and dislocates the dominant discursive construction of US and THEM, (a construction explained by Hall's concept of binary oppositions, detailed in Chapter 2). Bhabha uses the term "enunciation" as a linguistic metaphor for how cultural differences are articulated through discourse and thus how differences are discursively produced. Like Hall, Bhabha views culture as a process of understanding and of signification because Bhabha sees traditional cultures' struggle against colonizing cultures as transforming them. Adorno's theory of Standardization will be understood as a theoretical position of Western authority. The thesis will argue that Adorno's theory rests on the assumption that there is an "essence" to music, an essence that Adorno rationalizes as structure/form. The thesis will demonstrate that constructing music as possessing an essence is connected to ideology and power and in this regard, Adorno's Standardization theory is a discourse of White Western power. It will be argued that "essentialism" is at the root of Western "rationalization" of music, and that the definition of what constitutes music is an extension of Western racist "discourses" of the Other. The methodological framework of the thesis entails a) applying semiotics to each of the three songs examined and b) also applying Bhabha's model of the Third Space to each of the songs. In this thesis, semiotics specifically refers to Stuart Hall's retheorized semiotics, which recognizes the dual function of semiotics in the analysis of marginal racial/cultural identities, i.e., simultaneously represent embedded racial/cultural stereotypes, and the marginal raciaVcultural first person voice that disavows and thus reinscribes stereotyped identities. (Here, and throughout this thesis, "first person voice" is used not to denote the voice of the songwriter, but rather the collective voice of a marginal racial/cultural group). This dual function fits with Hall's and Bhabha's idea that cultural identity emerges out of cultural antagonism, cultural struggle. Bhabha's Third Space is also applied to each of the songs to show that cultural "struggle" between colonizers and colonized produces cultural hybridities, musically expressed as fusions of styles/sounds. The purpose of combining semiotics and postcolonialism in the three songs to be analyzed is to show that marginal popular music, produced by members of cultural and racial minorities, establishes cultural identity and resists racist discourse by overwriting identities of racial/cultural stereotypes with identities shaped by the first person voice enunciated in the Third Space, to produce identities of cultural hybridities. Semiotic codes of embedded "Black" and "Indian" stereotypes in each song's musical and lyrical text will be read and shown to be overwritten by the semiotic codes of the first person voice, which are decoded with the aid of postcolonial concepts such as "ambivalence," "hybridity" and "enunciation."
Resumo:
Experiential Learning Instruments (ELls) are employed to modify the leamer's apprehension and / or comprehension in experiential learning situations, thereby improving the efficiency and effectiveness of those modalities in the learning process. They involve the learner in reciprocally interactive and determining transactions with his/her environment. Experiential Learning Instruments are used to keep experiential learning a process rather than an object. Their use is aimed at the continual refinement of the learner's knowledge and skill. Learning happens as the leamer's awareness, directed by the use of Ells, comes to experience, monitor and then use experiential feedback from living situations in a way that facilitates knmvledge/skill acquisition, self-correction and refinement. The thesis examined the literature relevant to the establishing of a theoretical experiential learning framework within which ELls can be understood. This framework included the concept that some learnings have intrinsic value-knowledge of necessary information-while others have instrumental value-knowledge of how to learn. The Kolb Learning Cycle and Kolb's six characteristics of experiential learning were used in analyzing three ELls from different fields of learning-saxophone tone production, body building and interpersonal communications. The ELls were examined to determine their learning objectives and how they work using experiential learning situations. It was noted that ELls do not transmit information but assist the learner in attending to and comprehending aspects of personal experience. Their function is to telescope the experiential learning process.
Resumo:
In this single group, pretest/posttest design study the literacy level and self-concept of nine moderately mentally handicapped adults was assessed. The participants in the study were involved in reading lessons using the Ball-Stick-Bird reading system, a brainbased program. No significant differences were found in either literacy level or reading level after intervention. However, there were changes in reading behaviour. These changes occurred in the subskills ofdirectionality, letter-sound correspondence, wordreading, and use of reading materials.
Resumo:
Memory Mixed with Desire: A preliminary study of Philosophy and Literature in the works of Friedrich Nietzsche and Milan Kundera Robert Spinelli Brock University, Department of Philosophy This thesis studies intertextuality in the works of Friedrich Nietzsche and Milan Kundera through the primary themes of memory and forgetting. The thesis starts with two introductory chapters that delineate memory according to Nietzsche and Kundera respectively. From here, I move into a discussion of Nietzsche's Ubermensch as an example of the type of forgetting that Nietzsche sees as a cure for the overabundance of memory that has led to Christian morality. Next, I explore the Kunderan concept of kitsch as the polar opposite of what Nietzsche has sought in his philosophy, finishing the chapter by tying the two thinkers together in a Kunderan critique of Nietzsche. The thesis ends with a chapter devoted to the Eternal Return beginning with an exegesis of Nietzsche's idea and ending with a similar exegesis of Kundera's treatment of this thought. What I suggest in this chapter is that the Eternal Return might itself be a form of kitsch even in its attempt to revalue existence.
Resumo:
Introduction In Difference and Repetition, Deleuze compares and contrasts Kierkegaard's and Nietzsche's ideas of repetition. He argues that neither of them really give a representation of repetition. Repetition for them is a sort of selective task: the way in which they determine what is ethical and eternal. With Nietzsche, it is a theater of un belie f. ..... Nietzsche's leading idea is to found the repetition in the etemal return at once on the death of God and the dissolution of the self But it is a quite different alliance in the theater of faith: Kierkegaard dreams of alliance between a God and a self rediscovered. I Repetition plays a theatrical role in their thinking. It allows them to dramatically stage the interplay of various personnae. Deleuze does give a positive account ofKierkegaard's "repetition"; however, he does not think that Kierkegaard works out a philosophical model, or a representation of what repetition is. It is true that in the book Repetition, Constantin Constantius does not clearly and fully work out the concept of repetition, but in Sickness Unto Death, Kierkegaard gives a full explanation of the self and its temporality which can be connected with repetition. When Sickness Unto Death is interpreted according to key passages from Repetition and The Concept of Anxiety, a clear philosophical concept of repetition can be established. In my opinion, Kierkegaard's philosophy is about the task of becoming a self, and I will be attempting to show that he does have a model of the temporality of self-becoming. In Sickness Unto Death, Kierkegaard explains his notions of despair with reference to sin, self, self-becoming, faith, and repetition. Despair is a sickness of the spirit, of the self, and accordingly can take three forms: in despair not to be conscious of having a self (not despair in the strict sense); in despair not to will to be oneself; in despair to will to be oneself2 In relation to this definition, he defines a self as "a relation that relates itself to itself and in relating itself to itself relates to another.''3 Thus, a person is a threefold relationship, and any break in that relationship is despair. Despair takes three forms corresponding to the three aspects of a self s relation to itself Kierkegaard says that a selfis like a house with a basement, a first floor, and a second floor.4 This model of the house, and the concept of the stages on life's way that it illustrates, is central to Kierkegaard's philosophy. This thesis will show how he unpacks this model in many of his writings with different concepts being developed in different texts. His method is to work with the same model in different ways throughout his authorship. He assigns many of the texts to different pseudonyms, but in this thesis we will treat the model and the related concepts as being Kierkegaard's and not only the pseudonyms. This is justified as our thesis will show this modelremains the same throughout Kierkegaard's work, though it is treated in different ways by different pseudonyms. According to Kierkegaard, many people live in only the basement for their entire lives, that is, as aesthetes ("in despair not to be conscious of having a self'). They live in despair of not being conscious of having a self They live in a merely horizontal relation. They want to get what they desire. When they go to the first floor, so to speak, they reflect on themselves and only then do they begin to get a self In this stage, one acquires an ideology of the required and overcomes the strict commands of the desired. The ethical is primarily an obedience to the required whereas the aesthetic is an obedience to desire. In his work Fear and Trembling (Copenhagen: 1843), Johannes de Silentio makes several observations concerning this point. In this book, the author several times allows the desired ideality of esthetics to be shipwrecked on the required ideality of ethics, in order through these collisions to bring to light the religious ideality as the ideality that precisely is the ideality of actuality, and therefore just as desirable as that of esthetics and not as impossible as the ideality of ethics. This is accomplished in such a way that the religious ideality breaks forth in the dialectical leap and in the positive mood - "Behold all things have become new" as well as in the negative mood that is the passion of the absurd to which the concept "repetition" corresponds.s Here one begins to become responsible because one seeks the required ideality; however, the required ideality and the desired ideality become inadequate to the ethical individual. Neither of them satisfy him ("in despair not to will to be oneself'). Then he moves up to the second floor: that is, the mystical region, or the sphere of religiousness (A) ("despair to will to be oneself). Kiericegaard's model of a house, which is connected with the above definition ofdespair, shows us how the self arises through these various stages, and shows the stages of despair as well. On the second floor, we become mystics, or Knights of Infinite Resignation. We are still in despair because we despair ofthe basement and the first floor, however, we can be fiill, free persons only ifwe live on all the floors at the same time. This is a sort of paradoxical fourth stage consisting of all three floors; this is the sphere of true religiousness (religiousness (B)). It is distinguished from religiousness (A) because we can go back and live on all the floors. It is not that there are four floors, but in the fourth stage, we live paradoxically on three at once. Kierkegaard uses this house analogy in order to explain how we become a self through these stages, and to show the various stages of despair. Consequently, I will be explaining self-becoming in relation to despair. It will also be necessary to explain it in relation to faith, for faith is precisely the overcoming of despair. After explaining the becoming of the self in relation to despair and faith, I will then explain its temporality and thereby its repetition. What Kierkegaard calls a formula, Deleuze calls a representation. Unfortunately, Deleuze does not acknowledge Kierkegaard's formula for repetition. As we shall see, Kierkegaard clearly gives a formula for despair, faith, and selfbecoming. When viewed properly, these formulae yield a formula for repetition because when one hasfaith, the basement, firstfloor, and secondfloor become new as one becomes oneself The self is not bound in the eternity ofthe first floor (ethical) or the temporality of the basement (aesthete). I shall now examine the two forms of conscious despair in such a way as to point out also a rise in the consciousness of the nature of despair and in the consciousness that one's state is despair, or, what amounts to the same thing and is the salient point, a rise in the consciousness of the self The opposite to being in despair is to have faith. Therefore, the formula set forth above, which describes a state in which there is not despair at all, is entirely correct, and this formula is also the formula for faMi in ^elating itself to itself and in willing to be itself, the self rests transparently in the power that established it.
Resumo:
In this research study I examined how four principals of secondary schools interpreted authority and how these interpretations affected their practice. This study involved a presentation of the literature where the concept of qualitative methodology as well as general concepts of authority were reviewed. Four principals were interviewed and asked to reflect on their feelings and experiences as they related to the practice of authority. Five major themes emerged from their reflections and stories which were: Understandings of the Concept of Authority, Principals' Enactment of Authority, Thoughts and Experiences related to Challenges to Their Authority, A View of Principals' Challenge of Authority, and Changing Views on the Authority of Principals in Ontario. The stories of these four principals demonstrated that the practice of authority is complex, dynamic, and contains personal and social tensions. The sharing of these ideas and stories provided a window into the world of these secondary school educational leaders and their experiences with, and enactment of, authority. From this research four recommendations were made to improve educators' practice related to the issue of authority. The importance of this study is that it presents an understanding of the dynamic nature of the process and enactment of authority by these secondary school principals at a unique time in the history of education in Ontario.This qualitative research provides a snapshot of a particular group of educators at a particular time and place. Others need to add to these understandings and modify these ideas through further research. Understanding the experiences of educational leaders as they negotiate concepts of authority gives a window on this very complex, yet vital, component of education.
Resumo:
This thesis analyzes four philosophical questions surrounding Ibn al-'Arabi's concept of the al-iman al-kamil, the Perfect Individual. The Introduction provides a definition of Sufism, and it situates Ibn al-'Arabi's thought within the broader context of the philosophy of perfection. Chapter One discusses the transformative knowledge of the Perfect Individual. It analyzes the relationship between reason, revelation, and intuition, and the different roles they play within Islam, Islamic philosophy, and Sufism. Chapter Two discusses the ontological and metaphysical importance of the Perfect Individual, exploring the importance of perfection within existence by looking at the relationship the Perfect Individual has with God and the world, the eternal and non-eternal. In Chapter Three the physical manifestations of the Perfect Individual and their relationship to the Prophet Muhammad are analyzed. It explores the Perfect Individual's roles as Prophet, Saint, and Seal. The final chapter compares Ibn al-'Arabi's Perfect Individual to Sir Muhammad Iqbal's in order to analyze the different ways perfect action can be conceptualized. It analyzes the relationship between freedom and action.
Resumo:
"I began these pages for myself, in order to think out my own particular pattern of living, my own individual balance of life, work and human relationships." Lindbergh (1983) p.9. In this thesis, I use self-study research as I focus on the topic of living legacy. This is a personal story, using narrative methodology and method as a means of uncovering and naming life lessons learned. I write to gain insight into my interpretation of the concept of living legacy - what living legacy means to me and why this concept is significant to me - and how living legacy impacts the person that I am in the present. Using a narrative lens, I inquire into stories that connect me to my spirit, my gender, education and theology, through my living legacy lessons, and I seek the impact these stories hold for me in my life today. I utilize a variety of methods including personal journals, course work, and arts-based research experiences as I explore the connections to my emerging perceptions ofmy living legacy lessons. This thesis represents the beginning of a continuing journey of self-discovery. I take the journey in order to uncover hidden and ongoing lessons of living legacy and the impact they have on the student and educator that I am.
Resumo:
The new Physiotherapy and Occupational Therapy programmes, based in the Faculty of Health Sciences, McMaster University (Hamilton, Ontario) are unique. The teaching and learning philosophies utilized are based on learner-centred and selfdirected learning theories. The 1991 admissions process of these programmes attempted to select individuals who would make highly qualified professionals and who would have the necessary skills to complete such unique programmes. In order to: 1 . learn more about the concept of self-directed learning and its related characteristics in health care professionals; 2. examine the relationship between various student characteristics - personal, learner and those assessed during the admissions process - and final course grades, and 3. determine which, if any, smdent characteristics could be considered predictors for success in learner-centred programmes requiring self-directed learning skills, a correlational research design was developed and carried out. Thirty Occupational Therapy and thirty Physiotherapy smdents were asked to complete 2 instruments - a questionnaire developed by the author and the Oddi Continuing Learning Inventory (Oddi, 1986). Course grades and ratings of students during the admissions process were also obtained. Both questionnaires were examined for reliability, and factor analyses were conducted to determine construct validity. Data obtained from the questionnaires, course grades and student ratings (from the admissions process) were analyzed and compared using the Contingency Co-efficient, the Pearson's product-moment correlation co-efficient, and the multiple regression analysis model. The research findings demonstrated a positive relationship (as identified by Contingency Coefficient or Pearson r values) between various course grades and the following personal and learner characteristics: field of smdy of highest level of education achieved, level of education achieved, sex, marital stams, motivation for completing the programmes, reasons for eru-oling in the programmes, decision to enrol in the programmes, employment history, preferred learning style, strong selfconcept and the identification of various components of the concept of self-directed learning. In most cases, the relationships were significant to the 0.01 or 0.(X)1 levels. Results of the multiple regression analyses demonstrated that several learner and admissions characteristic variables had R^ values that accounted for the largest proportion of the variance in several dependent variables. Thus, these variables could be considered predictors for success. The learner characteristics included: level of education and strong self-concept. The admissions characteristics included: ability to evaluate strengths, ability to give feedback, curiosity and creativity, and communication skills. It is recommended that research continue to be conducted to substantiate the relationships found between course grades and characteristic variables in more diverse populations. "Success in self-directed programmes" from the learner's perspective should also be investigated. The Oddi Continuing Learning Inventory should continue to be researched. Further research may lead to refinement or further development of the instrument, and may provide further insight into self-directed learner attributes. The concept of self-directed learning continues to be incorporated into educational programmes, and thus should continue to be explored.
Resumo:
Educators continually look for strategies to enhance and improve the reading practices of their students. This is an especially challenging task for secondary level teachers as high school students often lack intrinsic motivation to read for pleasure (Bucher & Manning, 2004; Horton, 2005; Wooicott, Research Pty. Ltd. 2001). The purpose of this study was to detennine the effects of the Drop Everything and Read (D.E.A.R.) program on writing, on reading, and on grades, from the perspective of eight Grade 9 students. Of particular interest were the students' perceptions of the effect that participation in the program had on their grades, their writing, their motivation to reading, and their concept of themselves as readers. The eight participants were tracked over the course of a semester. Using qualitative research techniques, data were collected from four sources: two student surveys, researcher's daily field observations, students' weekly reading logs, and three open-ended one-on-one interviews. In order to gain an understanding of the impact of the D.E.A.R program, the data were corroborated, and analyzed with NVivo: N7 (2006). From the data analysis, five themes emerged as a function of the Grade 9 students' experiences in the D.E.A.R. program: Reading Preferences, Time Spent Reading, Making Associations with Reading for Pleasure, Perceptions of Self-as-Reader, and Evaluations of the D.E.A.R Program. In the interest of supporting students' positive reading habits and for the future implementation, these five themes are presented as a series of findings together with recommendations for practice.
Resumo:
ABSTRACT Canada is an aging society. The number of people aged sixty-five and over is rising, while the number of people under twenty is declining. These two concurrent changes in the age structure have produced a sh~ft in the demographic composition of Canada which is commonly referred to as the aging phenomenon. Regardless of whether or not the number of people under twenty continues to decline, the number of elderly in Canada will almost double over the next twenty years. This rapidly growing elderly clientele will doubtless have an impact on Canadian governments. Federal, provincial and municipal governments are presently providing a variety of programs that have a special bearing on the aged and most senior citizens are beneficiaries of one or more of these programs. The ramifications of a rapidly growing elderly clientele are obvious. In order to cope with the impact of a significant increase in the number of elderly persons, the development and implementation of aging policy must be co-ordinated at each level of government and between and among levels of government. If aging policy is not co-ordinated, the results are likely to be: inappropriate policy decisions; duplication and overlap; and, ineffective and irresponsive services. No one benefits from these results. The need for co-ordination is apparent. The purpose of this thesis is to examine existing governmental efforts to co-ordinate policy in the field of aging. These efforts are examined by focusing on interactions directed at co-ordination between and among major actors in aging policy. A framework is used to structure the description and analysis of these interactions. The variables of formalisation and intensity and the concept of power are instrumental in analysing interactions for co-ordination. The underlying intent of this thesis is to discover some of the main gaps in existing governmental efforts to co~ordinate aging policy. Gaps are, in fact, discovered. Several explanations for the existence of gaps in interactions for co-ordination are discussed. A major hypothesis involving a relationship between a bureaucratic form of organisation and interactions for coordination is suggested. Finally, three recommendations for improving co-ordination in aging policy are offered.
Resumo:
Do evaluation of the literature and a regional observational report support Dr. Feingold's claim that the K-P (Kaiser-Permanente) elimination diet improves the behaviours of hyperkinetic children, and others? Dr. Feingold suggests that some hyperkinetic children, and other children as well, are genetically predisposed to intolerance of food additives, particularly food colours and flavours. He claims that the K-P diet, that eliminates salicylates and artificial food colours and flavours, improves the hyperkinetic child's behaviour, muscle co-ordination, and scholastic performance. Public acceptance of the K-P diet has outstripped acceptance in the medical and scientific communities. Evaluation of available data and additional studies are needed to arrive at a conclusion of acceptance or rejection of the K-P diet for hyperkinetic children and others. My interest in the K-P elimination diet for hyperkinetic children is educational. My experience as an elementary school teacher in special education and in the classroom from K-8 has taught me that attentiveness is crucial to learning. Hyperkinesis appears to impair a child's ability to attend. Learning problems appear, followed by behavioural and social problems. l If we accept the possibility of a relationship between diet and attentiveness, and attentiveness and school behaviours, then the diet-behaviour link could be of lay importance. For instance, if a diet such as the K-P diet could do what is claimed, substantial benefits could accrue to the child. One could, for example, improve a child's behaviours. One could identify attending disturbances early in the child's education, possibly minimizing, or eliminating future difficulties in school. Finally, the greatest benefit may be the fulfillment of the basic goal of our Ontario schools, that the eh~ld-,lIla1p.evelop happily and competently within our educational framework. 2 This thesis reports evidence from the literature and from a regional observational investigation to determine the possibility of a link between the behaviours of children and Dr. Feingold's K-P elimination diet. The literature research examines (1) Dr. Feingold's concept of H-LD, (2) his K-P elimination diet, and (3) the response from three sectors, medicine, science, and the public. The regional investigation examines the observed behaviours of nine children in Regional Niagara during a nine-month period on the K-P diet.
Resumo:
The world of work with Western society appears to be undergoing a major change. The literature has described this phenomenon as a change from an industrialbased economy to a knowledge-based economy. This change will represent a complete transformation of the world of work; some suggest that everything we have come to accept and know as normal will change. Our present society seems to be in a period of transition. It is a time with many challenges and problems, many of which cannot be solved with thinking patterns from an old industrial-based economy. A fundamental shift in thinking patterns consistent with a new emerging world of work must take place. This change in thinking represents a fundmental shift from traditional and linear ways of seeing the world (worldview), to more holistic ways of seeing the world. In this investigation the word paradigm was used to define how people see their world. A paradigm shift is defined as a change in how a person sees their world: a change from an old to new or different way of viewing the world. Those individuals who are the first to shift their paradigm are called paradigm pioneers. These individuals do not only shift their ways of seeing the world, but they also begin to act and behave in ways consistent with the new paradigm. Thus far the research literature has adequately described the concepts of paradigms and paradigm shifts. However, little is known regarding how people actually and eventually make a shift. As it will be important for each individual to make a personal paradigm shift, then it will be extremely valuable to learn more about the process itself. The purpose of this investigation was to explore these issues in more detail and specifically, describe the experience of paradigm shifts and explore the experience of paradigm pioneers. A qualitative research methodology involving in-depth interviews was used to investigate the experiences of four participants identified as paradigm pioneers. It is interesting to note that the participants in this study did not describe an allencompassing paradigm shift. In fact, each participant, defined a paradigm shift in several different ways. They did relate several examples of paradigm shifts. However, even among these examples, there was a high degree of variability. The findings of this investigation centered upon the participants' experience as pioneers. Each pioneer shared many of the same qualities, the first quality of which described how these pioneers dealt with change. I called this a change-sense quality. The pioneers viewed change in an open and positive manner, and were also aware of change taking place in their world. Finally, they displayed an understanding of change, and a bias to take positive action in the face it. The participants also shared an inner quality. The four pioneers demonstrated a personal purpose and vision, and were selfdirected individuals. They also had an innate curiosity which translated into a love of learning. They also displayed a quality where relationships with others were highly valued. Relationships were important to the pioneers because they played a support role to help them deal with the challenges of being a pioneer. Pioneers also valued relationships because, they relied on others to make change happen. The above mentioned qualities enabled pioneers to be effective in a changing world of work. The findings from this investigation have many implications for research and practice. First, the concept of paradigms and paradigm shifts must be further researched. A great deal more must be learned in order to better understand the kind of shift individuals must make to be effective in the new world of work. Second, the qualities displayed by pioneers are important for all members of the world of work to develop. The qualities shared by pioneers appeared to represent an enduring set of traits that can possibly help individuals deal more positively with uncertainty and rapid change taking place in today's North American world of work.
Resumo:
Exchange reactions between molecular complexes and excess acid
or base are well known and have been extensively surveyed in the
literature(l). Since the exchange mechanism will, in some way
involve the breaking of the labile donor-acceptor bond, it follows
that a discussion of the factors relating to bonding in molecular complexes
will be relevant.
In general, a strong Lewis base and a strong Lewis acid form a
stable adduct provided that certain stereochemical requirements are
met.
A strong Lewis base has the following characteristics (1),(2)
(i) high electron density at the donor site.
(ii) a non-bonded electron pair which has a low ionization potential
(iii) electron donating substituents at the donor atom site.
(iv) facile approach of the site of the Lewis base to the
acceptor site as dictated by the steric hindrance of the
substituents.
Examples of typical Lewis bases are ethers, nitriles, ketones,
alcohols, amines and phosphines.
For a strong Lewis acid, the following properties are important:(
i) low electron density at the acceptor site.
(ii) electron withdrawing substituents. (iii) substituents which do not interfere with the close
approach of the Lewis base.
(iv) availability of a vacant orbital capable of accepting
the lone electron pair of the donor atom.
Examples of Lewis acids are the group III and IV halides such
(M=B, AI, Ga, In) and MX4 - (M=Si, Ge, Sn, Pb).
The relative bond strengths of molecular complexes have been
investigated by:-
(i)
(ii)
(iii)
(iv)
(v]
(vi)
dipole moment measurements (3).
shifts of the carbonyl peaks in the IIIR. (4) ,(5), (6) ..
NMR chemical shift data (4),(7),(8),(9).
D.V. and visible spectrophotometric shifts (10),(11).
equilibrium constant data (12), (13).
heats of dissociation and heats of reactions (l~),
(16), (17), (18), (19).
Many experiments have bben carried out on boron trihalides in
order to determine their relative acid strengths. Using pyridine,
nitrobenzene, acetonitrile and trimethylamine as reference Lewis
bases, it was found that the acid strength varied in order:RBx3 >
BC1
3 >BF 3
• For the acetonitrile-boron trihalide and trimethylamine
boron trihalide complexes in nitrobenzene, an-NMR study (7) showed
that the shift to lower field was. greatest for the BB~3 adduct ~n~
smallest for the BF 3 which is in agreement with the acid strengths. If electronegativities of the substituents were the only
important effect, and since c~ Br ,one would expect
the electron density at the boron nucleus to vary as BF3
Resumo:
We developed the concept of split-'t to deal with the large molecules (in terms of the number of electrons and nuclear charge Z). This naturally leads to partitioning the local energy into components due to each electron shell. The minimization of the variation of the valence shell local energy is used to optimize a simple two parameter CuH wave function. Molecular properties (spectroscopic constants and the dipole moment) are calculated for the optimized and nearly optimized wave functions using the Variational Quantum Monte Carlo method. Our best results are comparable to those from the single and double configuration interaction (SDCI) method.