960 resultados para Attribute Assignment
Resumo:
Six sigma is a quality improvement philosophy with systematic and formal approach. In order to successfully implement and utilize six sigma the basic disciplines of it should be adopted by the entire organization. Furthermore, employee involvement is crucial in six sigma implementation. This thesis addresses the challenges of long-lasting involvement in the case company. It focuses on gaps of involving six sigma trained employees, Black Belts. Theoretical framework of the thesis illustrates different factors influencing employee involvement. Influencing factors can be divided into ten categories: organizational culture, managerial commitment, leadership style, employee empowerment, employees’ perceptions, communication, training, goals, performance measurement and incentives. Factors and categories overlap and are related to each other. The framework provides holistic view of employee involvement in six sigma context but can be used also with other quality management philosophies. This thesis was conducted as a case study and written on an assignment to a power and automation technology company. Due to the nature of research problem, the data collection was conducted by interviewing case company personnel. In order to study involvement from employees’ point of view interview questions were designed to be open-ended and to allow the interviewees to tell freely about the phenomenon. This thesis provides empirical support on previous studies in organizational support, management commitment and employee empowerment. In addition, it indicates the importance of separate function for Black Belts in the organization. The gaps in Black Belt involvement can be categorized under two categories: Management driven gaps are related to management commitment, organizational structure and culture and information systems. Black Belt driven gaps are related to practice and effort of using six sigma. This thesis finds solutions for bridging these gaps in the case company by applying findings from literature research and suggestions given by the interviewees. For each gap, actions are suggested for bridging the discrepancy between current and desired situations. The thesis states that in order to embed six sigma in the organization the most crucial gaps, lack of management commitment, six sigma vision and possibilities to use six sigma, should be diminished.
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The starting point of this essay is to show that, in our view, the problem of the traditional economics is not in the deductive method nor the mathematical methods used, but to attribute to economic agents "power" on the future and prescribe the existence of ergodic stochastic processes in their economic analyzes. Thus, building a theory on the ground whose bases are not able to sustain a proper understanding of the world, mainstream economics has difficulties in using the modeling for establishing deductions and conclusions that help understanding the system. Thus, the logical-mathematical rigor in economic models and deduction can be used with appropriate axioms, which is not the case of mainstream economics. Our hypothesis is that the inability of the mainstream in predicting economic crisis is due to the non-recognition of some principles that best describe the dynamics of financialized contemporary capitalism, as the principles of non-ergodicity and Keynesian uncertainty.
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Under EU competition law, parent companies may be held jointly and severally liable for the competition law infringements committed by their subsidiaries. The possibility of holding parent companies liable demonstrates a significant exception from the idea of separate legal entities. However, it is not the only deviation developed under EU competition law. In cases, where the legal entity responsible for the anti-competitive conduct has changed its form, liability can be attributed to the new operator, in particular, to its successor. The principles of legal certainty and legitimate expectations are issues that surround the doctrines of parental and successor liability. The aim of this thesis is to present a comprehensive comparative analysis of the parental and successor liability doctrines and to clarify the conditions under which it is possible to attribute liability for the infringements of EU competition law. The main purpose is therefore to demonstrate the problems related to the allocation of liability and to discuss whether these liability principles, established to assure the effective enforcement of the EU competition rules, are good solutions. The research methods used in this thesis are the legal dogmatic approach and the comparative law approach. The former enables the possibility of using the case law and legislation as a framework in which the difficulties concerning the application of parental and successor liability can be discussed while the latter ensures the comparison of the characteristics and judgments. The doctrines of parental and successor liability are both well established, but the application practice has caused several difficulties. These problems derive from, inter alia, the broadness and disjointed developed of the doctrines. There has been much recent case law dealing with these issues and having the potential to open up a considerable risk and to allocate strict liability for parent and successor companies.
Resumo:
Tämän tutkielman tavoite on yrityksen tulevan menestymisen tai epäonnistumisen ennustaminen. Tutkimuksen kohteena ovat tutkimus ja kehitys rahoitusta vuosina 2007- 2012 Tekesiltä saaneet mikro- ja pk yritykset. Ennustusta pyrittiin tekemään näille yrityksille niiden rahoitusprojektien alkuhetkeltä (hakemushetki). Tutkimus toteutettiin toimeksiantona Tekesille ja se jatkaa aikaisempaa tutkielmaa, ”Onko projektin henkilöriskitasolla tai talousriskitasolla yhteyttä t&k- projektin onnistumiseen?”. Tämän tutkimuksen johtopäätös oli, ettei varsinkaan talousriskillä ja projektin onnistumisella ole yhteyttä ja sen vuoksi niistä tarvittiin lisää tietoa. Teoreettisessa osuudessa käsitellään yrityksen kasvua ja onnistumisen tai epäonnistumisen ennakointia. Teoria pohjautuu aiheen aikaisempaan kirjallisuuteen ja sen tarkoitus on pohjustaa tutkielmassa tehtyjä valintoja yrityksien menestymisen ennustamiseksi. Tutkimus on toteutettu kvantitatiivisena tutkimuksena. Aineisto koostuu 430 Tekesin t&k- rahoitusta saaneista mikro- ja pk yrityksistä. Empiirisen osuuden tarkoitus oli selvittää, voidaanko koko yrityksen, menestystä ennustaa, jotta rahoitus voidaan kohdistaa paremmin, eli selvittää minkälaisia yrityksiä tulisi rahoittaa, jotta rahoitus kohdistuisi menestyjille. Tämän lisäksi tutkimuksessa haluttiin löytää oikeat muuttujat, joiden avulla yrityksen menestymisen ennustaminen on mahdollista. Menestymisen haluttiin kuvaavan koko yrityksen liiketoiminnan menestymistä. Menestymisen mittariksi valittiin liikevaihdon kasvu ja tarkasteltavaksi ajanjaksoksi aika yrityksen t&k- projektin hakemusvaiheesta, kolmen vuoden päähän projektin päättymisestä. Yritykset jaettiin menestyjiin liikevaihdon kasvun mukaan, ja niistä luotiin neljä koria: “Huiput”, “Kasvut”, “Hiipujat” ja “Konkurssit” ja koreja lähdettiin tutkimaan erilaisten mittarien avulla. Valitut mittarit olivat Tekesin riskiarvio (talousriski, henkilöriski, kehitysriski ja markkinariski), tilinpäätöksen tunnusluvuista kannattavuuden, maksuvalmiuden ja vakavaraisuuden tunnusluvut (liikevoittoprosentti ja sijoitetun pääoman tuottoprosentti, quick ratio ja omavaraisuusaste), projektin omarahoitus (yrityksen hakemusvaiheessa ilmoittama muun rahoituksen lähde, joka voi olla vieraanpääoman ehtoista, oman pääomanehtoista tai tulorahoitusta), sekä muut mittarit (uutuusarvo, jalostusarvo, tuottavuus ja lainojen perimättäjättöhakemukset). Riippumattomuutta testattiin ristiintaulukoinnilla, khiin neliötestillä ja kontingenssikerroin C:n avulla omavaraisuusasteen tunnusluvun osalta yhdistämällä ”Huiput”, ”Kasvut” ja ”Hiipujat” yhteen kotiin ja vertaamalla niitä konkurssiin menneisiin yrityksiin. Lopuksi konkurssiennusteista testattiin pienille yrityksille tarkoitettua Laitisen yhdistelmälukua. Tutkimuksessa havaittiin seuraavaa. Parhaiten yrityksen tulevan kasvun tai konkurssin ennakoivat havainnot seuraavissa muuttujissa: onko hanke rahoitettu lainalla vai avustuksella sekä mikä yrityksen hakemusvaiheen omavaraisuusaste, omarahoitusosuus tai tuottavuus on. Yrityksen hyvä rahatilanne projektin hakemusvaiheessa ei ennusta yrityksen liikevaihdon kasvua. Täydellistä ennustetta kasvulle ei voida tehdä. Laitisen yhdistelmäluku koettiin heikoksi tunnusluvuksi konkurssia ennustettaessa. Tämän takia, sitä muokattiin eri tavoin parhaan mahdollisemman ennusteen saamiseksi. Paras lopputulos saatiin muuttamalla tunnusluvun kriittistä arvoa pienemmäksi.
Resumo:
This thesis was conducted on assignment by a multinational chemical corporation as a case study. The purpose of this study is to find ways to improve the purchasing process for small purchases at the case company. The improvements looked after are mainly cost and time savings. Purchasing process is the process that starts from the requisition of goods or services and ends when the invoice is paid. In this thesis the purchases with value less than 1000€ are considered to be small. The theoretical framework of the thesis consists of general theoretical view of costs and performance of the purchasing process, different types of purchasing processes and a model for improving purchasing processes. The categorization to small and large purchases is the most important followed by the division between direct and indirect purchases. Also models that provide more strategic perspective for categorization were found to be useful. Auditing and managerial control are important parts of the purchasing process. When considering the transaction costs of purchasing from the costs–benefits perspective large and small purchases should not have the same processes. Purchasing cards, e-procurement and vendor managed inventory are seen as an alternative to the traditional purchasing process. The empirical data collection was done by interviewing the company employees that take part of the purchasing process in their daily work. The interviews had open-ended questions and the answers were coded and analyzed. The results consist of process description and assessment as well as suggestions for potential improvements. At the case company the basic purchasing process was similar to the traditional purchasing process that is entirely done with computers and online. For some categories there was already more sophisticated e-procurement solutions in use. To improve the current e-procurement based solutions elimination of authorization workflow and better information exchange can be seen as potential improvements for most of the case purchases. Purchasing cards and a lightweight form of vendor managed inventory can be seen as potential improvements for some categories. Implementing the changes incurs at least some cost and the benefits might be hard to measure. This thesis has revealed that the small purchases have potential for significant cost and time savings at the case company.
Resumo:
Polarized reflectance measurements of the quasi I-D charge-transfer salt (TMTSFh CI04 were carried out using a Martin-Puplett-type polarizing interferometer and a 3He refrigerator cryostat, at several temperatures between 0.45 K and 26 K, in the far infrared, in the 10 to 70 cm- 1 frequency range. Bis-tetramethyl-tetraselena-fulvalene perchlorate crystals, grown electrochemically and supplied by K. Behnia, of dimensions 2 to 4 by 0.4 by 0.2 mm, were assembled on a flat surface to form a mosaic of 1.5 by 3 mm. The needle shaped crystals were positioned parallel to each other along their long axis, which is the stacking direction of the planar TMTSF cations, exposing the ab plane face (parallel to which the sheets of CI04 anions are positioned). Reflectance measurements were performed with radiation polarized along the stacking direction in the sample. Measurements were carried out following either a fast (15-20 K per minute) or slow (0.1 K per minute) cooling of the sample. Slow cooling permits the anions to order near 24 K, and the sample is expected to be superconducting below 1.2 K, while fast cooling yields an insulating state at low temperatures. Upon the slow cooling the reflectance shows dependence with temperature and exhibits the 28 cm- 1 feature reported previously [1]. Thermoreflectance for both the 'slow' and 'fast' cooling of the sample calculated relative to the 26 K reflectance data indicates that the reflectance is temperature dependent, for the slow cooling case only. A low frequency edge in the absolute reflectance is assigned an electronic origin given its strong temperature dependence in the relaxed state. We attribute the peak in the absolute reflectance near 30 cm-1 to a phonon coupled to the electronic background. Both the low frequency edge and the 30 cm-1 feature are noted te shift towards higher frequcncy, upon cntering the superconducting state, by an amount of the order of the expected superconducting energy gap. Kramers-Kronig analysis was carried out to determine the optical conductivity for the slowly cooled sample from the measured reflectance. In order to do so the low frequency data was extrapolated to zero frequency using a Hagen-Ru bens behaviour, and the high frequency data was extended with the data of Cao et al. [2], and Kikuchi et al. [3]. The real part of the optical conductivity exhibits an asymmetric peak at 35 cm-1, and its background at lower frequencies seems to be losing spectral weight with lowering of the temperature, leading us to presume that a narrow peak is forming at even lower frequencies.
Resumo:
The perovskite crystal structure is host to many different materials from insulating to superconducting providing a diverse range of intrinsic character and complexity. A better fundamental description of these materials in terms of their electronic, optical and magnetic properties undoubtedly precedes an effective realization of their application potential. SmTiOa, a distorted perovskite has a strongly localized electronic structure and undergoes an antiferromagnetic transition at 50 K in its nominally stoichiometric form. Sr2Ru04 is a layered perovskite superconductor (ie. Tc % 1 K) bearing the same structure as the high-tem|>erature superconductor La2_xSrrCu04. Polarized reflectance measurements were carried out on both of these materials revealing several interesting features in the far-infrared range of the spectrum. In the case of SmTiOa, although insulating, evidence indicates the presence of a finite background optical conductivity. As the temperature is lowered through the ordering temperature a resonance feature appears to narrow and strengthen near 120 cm~^ A nearby phonon mode appears to also couple to this magnetic transition as revealed by a growing asymmetry in the optica] conductivity. Experiments on a doped sample with a greater itinerant character and lower Neel temperature = 40 K also indicate the presence of this strongly temperature dependent mode even at twice the ordering temperature. Although the mode appears to be sensitive to the magnetic transition it is unclear whether a magnon assignment is appropriate. At very least, evidence suggests an interesting interaction between magnetic and electronic excitations. Although Sr2Ru04 is highly anisotropic it is metallic in three-dimensions at low temperatures and reveals its coherent transport in an inter-plane Drude-like component to the highest temperatures measured (ie. 90 K). An extended Drude analysis is used to probe the frequency dependent scattering character revealing a peak in both the mass enhancement and scattering rate near 80 cm~* and 100 cm~* respectively. All of these experimental observations appear relatively consistent with a Fermi-liquid picture of charge transport. To supplement the optical measurements a resistivity station was set up with an event driven object oriented user interface. The program controls a Keithley Current Source, HP Nano-Voltmeter and Switching Unit as well as a LakeShore Temperature Controller in order to obtain a plot of the Resistivity as a function of temperature. The system allows for resistivity measurements ranging from 4 K to 290 K using an external probe or between 0.4 K to 295 K using a Helium - 3 Cryostat. Several materials of known resistivity have confirmed the system to be robust and capable of measuring metallic samples distinguishing features of several fiQ-cm.
Resumo:
The 5a-reductase of Penicillium decumbens ATCC 10436 was used as a model for the mammalian enzyme to investigate the mechanism of reduction of testosterone to 5adihydrotestosterone . The purpose of this study was to search for specific 5a-reductase inhibitors which antagonize prostate cancer . In a whole-cell biotransformation mode, this organism reduced testosterone (1) to 5a-dihydrosteroids (8) and 5aandrostane- 3, 17-dione (9) in yields of 28% and 37% respectively. Control experiments have shown that 5aandrostane- 3, 17-dione (9) can be produced from the corresponding alcohol (8) in a subsequent reaction separate from that catalysed by the 5a-reductase enzyme . Androst-4- ene-3, 17-dione (2) is reduced to give only (9) with a recovery of 80% The stereochemistry of the reduction was determined by 500 MHz ^H NMR analysis of the products resulting from the deuterium labelled substrates. The results were obtained by an analysis of the NOE difference spectra, double-quantum filtered phase sensitive COSY 2-D spectra, and ^^c-Ir 2-D shift correlation spectra of deuterium labelled products. According to the unambiguous assignment of the signals due to H-4a and H-4Ii in 5a-dihydro steroids, the NMR data show clearly that addition of hydrogen to the 4{5)K bond has occurred in a trans manner at positions 413 and 5a. To Study the reduction mechanism of this enzyme, several substrates were prepared as following; 3-methyleneandrost-4-en- 17fi-ol(3), androst-4-en-17i5-ol(5) , androst-4-en-3ii, 17fi-diol (6) and 4, 5ii-epoxyandrostane-3, 17-dione (7) . Results suggest that this enzyme system requires an oxygen atom at the 3-position of the steroid in order to bind the substrate. Furthermore, the mechanism of this 5a-reductase may proceed via direct addition of hydrogen at the 4,5 position without involvement of a carbonyl group as an intermediate.
Resumo:
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.
Resumo:
TITLE: The normal co-ordinate analysis, vibrational spectra and theoretical infrared intensities of some thiocarbonyl halides. AUTHOR: J. L. Brema SUPERVISOR: Dr. D. C. Moule NUMBER OF PAGES: 89 ABSTRACT: The vibrational assignment of the five-in-plane fundamental modes of CSClBr has been made on the basis of infrared gas phase and liquid Raman spectral analyses to supplement our earlier vibrational studies. Even though the one out-of-plane fundamental was not observed spectroscopically an attempt has been made to predict its frequency. The vibrational spectra contained impurity bands and the CSClBr assignment was made only after a thorough analysis of the impurities themselves. A normal co-ordinate analysis calculation was performed assuming a Urey-Bradley force field. This calculation yielded the fundamental frequencies in good agreement with those observed after refinement of the originally transferred force constants. The theoretical frequencies are the eigenvalues of the secular equation and the calculation also gave the corresponding eigenvectors in the form of the very important LLj matrix. The [l] matrix is the transfoirmation between internal co-ordinates and normal co-ordinates and it is essential for Franck-Condon calculations on electronically excited molecules and for infrared Integrated band intensity studies. Using a self-consistent molecular orbital calculation termed "complete neglect of differential overlap" (CNDO/2) , theoretical values of equilibrium bond lengths and angleswere calcuted for a series of carbonyl and thlocarbonyl molecules. From these calculations valence force field force constants were also determined but with limited success. With the CNIX)/2 method theoretical dipole moment derivatives with respect to symmetrized internal co-ordinates were calculated and the results should be useful in a correlation with experimentally determined values.
Resumo:
It is our intention in the course of the development of this thesis to give an account of how intersubjectivity is "eidetically" constituted by means of the application of the phenomenological reduction to our experience in the context of the thought of Edmund Husserl; contrasted with various representative thinkers in what H. Spiegelberg refers to as "the wider scene" of phenomenology. That is to say, we intend to show those structures of both consciousness and the relation which man has to the world which present themselves as the generic conditions for the possibility of overcoming our "radical sol itude" in order that we may gain access to the mental 1 ife of an Other as other human subject. It is clear that in order for us to give expression to these accounts in a coherent manner, along with their relative merits, it will be necessary to develop the common features of any phenomenological theory of consdousness whatever. Therefore, our preliminary inquiry, subordinate to the larger theme, shall be into some of the epistemological results of the application of the phenomenological method used to develop a transcendental theory of consciousness. Inherent in this will be the deliniation of the exigency for making this an lIintentional ll theory. We will then be able to see how itis possible to overcome transcendentally the Other as an object merely given among other merely given objects, and further, how this other is constituted specifically as other ego. The problem of transcendental intersubjectivity and its constitution in experience can be viewed as one of the most compelling, if not the most polemical of issues in phenomenology. To be sure, right from the beginning we are forced to ask a number of questions regarding Husserl's responses to the problem within the context of the methodological genesis of the Cartesian Meditations, and The Crisis of European Sciences and Transcendental Phenomenology. This we do in order to set the stage for amplification. First, we ask, has Husserl lived up to his goal, in this connexion, of an apodictic result? We recall that in his Logos article of 1911 he adminished that previous philosophy does not have at its disposal a merely incomplete and, in particular instances, imperfect doctrinal system; it simply has none whatever. Each and every question is herein controverted, each position is a matter of individual conviction, of the interpretation given byaschool, of a "point of view". 1. Moreover in the same article he writes that his goal is a philosophical system of doctrine that, after the gigantic preparatory work. of generations, really be- . gins from the ground up with a foundation free from doubt and rises up like any skilful construction, wherein stone is set upon store, each as solid as the other, in accord with directive insights. 2. Reflecting upon the fact that he foresaw "preparatory work of generations", we perhaps should not expect that he would claim that his was the last word on the matter of intersubjectivity. Indeed, with 2. 'Edmund Husserl, lIPhilosophy as a Rigorous Science" in Phenomenology and theCrisis6fPhilosophy, trans". with an introduction by Quentin Lauer (New York.: Harper & Row, 1965) pp. 74 .. 5. 2Ibid . pp. 75 .. 6. 3. the relatively small amount of published material by Husserl on the subject we can assume that he himself was not entirely satisfied with his solution. The second question we have is that if the transcendental reduction is to yield the generic and apodictic structures of the relationship of consciousness to its various possible objects, how far can we extend this particular constitutive synthetic function to intersubjectivity where the objects must of necessity always remain delitescent? To be sure, the type of 'object' here to be considered is unlike any other which might appear in the perceptual field. What kind of indubitable evidence will convince us that the characteristic which we label "alter-ego" and which we attribute to an object which appears to resemble another body which we have never, and can never see the whole of (namely, our own bodies), is nothing more than a cleverly contrived automaton? What;s the nature of this peculiar intentional function which enables us to say "you think just as I do"? If phenomenology is to take such great pains to reduce the takenfor- granted, lived, everyday world to an immanent world of pure presentation, we must ask the mode of presentation for transcendent sub .. jectivities. And in the end, we must ask if Husserl's argument is not reducible to a case (however special) of reasoning by analogy, and if so, tf this type of reasoning is not so removed from that from whtch the analogy is made that it would render all transcendental intersubjective understandtng impos'sible? 2. HistoticalandEidetic Priority: The Necessity of Abstraction 4. The problem is not a simple one. What is being sought are the conditions for the poss ibili:ty of experi encing other subjects. More precisely, the question of the possibility of intersubjectivity is the question of the essence of intersubjectivity. What we are seeking is the absolute route from one solitude to another. Inherent in this programme is the ultimate discovery of the meaning of community. That this route needs be lIabstract" requires some explanation. It requires little explanation that we agree with Husserl in the aim of fixing the goal of philosophy on apodictic, unquestionable results. This means that we seek a philosophical approach which is, though, not necessarily free from assumptions, one which examines and makes explicit all assumptions in a thorough manner. It would be helpful at this point to distinguish between lIeidetic ll priority, and JlhistoricallJpriority in order to shed some light on the value, in this context, of an abstraction.3 It is true that intersubjectivity is mundanely an accomplished fact, there havi.ng been so many mi.llions of years for humans to beIt eve in the exi s tence of one another I s abili ty to think as they do. But what we seek is not to study how this proceeded historically, but 3Cf• Maurice Natanson;·TheJburne in 'Self, a Stud in Philoso h and Social Role (Santa Cruz, U. of California Press, 1970 . rather the logical, nay, "psychological" conditions under which this is possible at all. It is therefore irrelevant to the exigesis of this monograph whether or not anyone should shrug his shoulders and mumble IIwhy worry about it, it is always already engaged". By way of an explanation of the value of logical priority, we can find an analogy in the case of language. Certainly the language 5. in a spoken or written form predates the formulation of the appropriate grammar. However, this grammar has a logical priority insofar as it lays out the conditions from which that language exhibits coherence. The act of formulating the grammar is a case of abstraction. The abstraction towards the discovery of the conditions for the poss; bi 1 ity of any experiencing whatever, for which intersubjective experience is a definite case, manifests itself as a sort of "grammar". This "grammar" is like the basic grammar of a language in the sense that these "rulesil are the ~ priori conditions for the possibility of that experience. There is, we shall say, an "eidetic priority", or a generic condition which is the logical antecedent to the taken-forgranted object of experience. In the case of intersubjectivity we readily grant that one may mundanely be aware of fellow-men as fellowmen, but in order to discover how that awareness is possible it is necessary to abstract from the mundane, believed-in experience. This process of abstraction is the paramount issue; the first step, in the search for an apodictic basis for social relations. How then is this abstraction to be accomplished? What is the nature of an abstraction which would permit us an Archimedean point, absolutely grounded, from which we may proceed? The answer can be discovered in an examination of Descartes in the light of Husserl's criticism. 3. The Impulse for Scientific Philosophy. The Method to which it Gives Rise. 6. Foremost in our inquiry is the discovery of a method appropriate to the discovery of our grounding point. For the purposes of our investigations, i.e., that of attempting to give a phenomenological view of the problem of intersubjectivity, it would appear to be of cardinal importance to trace the attempt of philosophy predating Husserl, particularly in the philosophy of Descartes, at founding a truly IIscientific ll philosophy. Paramount in this connexion would be the impulse in the Modern period, as the result of more or less recent discoveries in the natural sciences, to found philosophy upon scientific and mathematical principles. This impulse was intended to culminate in an all-encompassing knowledge which might extend to every realm of possible thought, viz., the universal science ot IIMathexis Universalis ll •4 This was a central issue for Descartes, whose conception of a universal science would include all the possible sciences of man. This inclination towards a science upon which all other sciences might be based waS not to be belittled by Husserl, who would appropriate 4This term, according to Jacab Klein, was first used by Barocius, the translator of Proclus into Latin, to designate the highest mathematical discipline. . 7. it himself in hopes of establishing, for the very first time, philosophy as a "rigorous science". It bears emphasizing that this in fact was the drive for the hardening of the foundations of philosophy, the link between the philosophical projects of Husserl and those of the philosophers of the modern period. Indeed, Husserl owes Descartes quite a debt for indicating the starting place from which to attempt a radical, presupositionless, and therefore scientific philosophy, in order not to begin philosophy anew, but rather for the first time.5 The aim of philosophy for Husserl is the search for apodictic, radical certitude. However while he attempted to locate in experience the type of necessity which is found in mathematics, he wished this necessity to be a function of our life in the world, as opposed to the definition and postulation of an axiomatic method as might be found in the unexpurgated attempts to found philosophy in Descartes. Beyond the necessity which is involved in experiencing the world, Husserl was searching for the certainty of roots, of the conditi'ons which underl ie experience and render it pOssible. Descartes believed that hi~ MeditatiOns had uncovered an absolute ground for knowledge, one founded upon the ineluctable givenness of thinking which is present even when one doubts thinking. Husserl, in acknowledging this procedure is certainly Cartesian, but moves, despite this debt to Descartes, far beyond Cartesian philosophy i.n his phenomenology (and in many respects, closer to home). 5Cf. Husserl, Philosophy as a Rigorous Science, pp. 74ff. 8 But wherein lies this Cartesian jumping off point by which we may vivify our theme? Descartes, through inner reflection, saw that all of his convictions and beliefs about the world were coloured in one way or another by prejudice: ... at the end I feel constrained to reply that there is nothing in a all that I formerly believed to be true, of which I cannot in some measure doubt, and that not merely through want of thought or through levity, but for reasons which are very powerful and maturely considered; so that henceforth I ought not the less carefully to refrain from giving credence to these opinions than to that which is manifestly false, if I desire to arrive at any certainty (in the sciences). 6 Doubts arise regardless of the nature of belief - one can never completely believe what one believes. Therefore, in order to establish absolutely grounded knowledge, which may serve as the basis fora "universal Science", one must use a method by which one may purge oneself of all doubts and thereby gain some radically indubitable insight into knowledge. Such a method, gescartes found, was that, as indicated above by hi,s own words, of II radical doubt" which "forbids in advance any judgemental use of (previous convictions and) which forbids taking any position with regard to their val idi'ty. ,,7 This is the method of the "sceptical epoche ll , the method of doubting all which had heretofor 6Descartes,Meditations on First Philosophy, first Med., (Libera 1 Arts Press, New York, 1954) trans. by L. LaFl eur. pp. 10. 7Husserl ,CrisiS of Eliroeari SCiences and Trariscendental Phenomenology, (Northwestern U. Press, Evanston, 1 7 ,p. 76. 9. been considered as belonging to the world, including the world itself. What then is left over? Via the process of a thorough and all-inclusive doubting, Descartes discovers that the ego which performs the epoche, or "reduction", is excluded from these things which can be doubted, and, in principle provides something which is beyond doubt. Consequently this ego provides an absolute and apodictic starting point for founding scientific philosophy. By way of this abstention. of bel ief, Desca'rtes managed to reduce the worl d of everyday 1 ife as bel ieved in, to mere 'phenomena', components of the rescogitans:. Thus:, having discovered his Archimedean point, the existence of the ego without question, he proceeds to deduce the 'rest' of the world with the aid of innate ideas and the veracity of God. In both Husserl and Descartes the compelling problem is that of establ ishing a scientific, apodictic phi'losophy based upon presuppos itionless groundwork .. Husserl, in thi.s regard, levels the charge at Descartes that the engagement of his method was not complete, such that hi.S: starting place was not indeed presupositionless, and that the validity of both causality and deductive methods were not called into question i.'n the performance of theepoche. In this way it is easy for an absolute evidence to make sure of the ego as: a first, "absolute, indubitablyexisting tag~end of the worldll , and it is then only a matter of inferring the absolute subs.tance and the other substances which belon.g to the world, along with my own mental substance, using a logically val i d deductive procedure. 8 8Husserl, E.;' Cartesian 'Meditation;, trans. Dorion Cairns (Martinus Nijhoff, The Hague, 1970), p. 24 ff.
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Silicon carbide, which has many polytypic modifications of a very simple and very symmetric structure, is an excellent model system for exploring, the relationship between chemical shift, long-range dipolar shielding, and crystal structure in network solids. A simple McConnell equation treatment of bond anisotropy effects in a poly type predicts chemical shifts for silicon and carbon sites which agree well with the experiment, provided that contributions from bonds up to 100 A are included in the calculation. The calculated chemical shifts depend on three factors: the layer stacking sequence, electrical centre of gravity, and the spacings between silicon and carbon layers. The assignment of peaks to lattice sites is proved possible for three polytypes (6H, 15R, and 3C). The fact that the calculated chemical shifts are very sensitive to layer spacings provides us a potential way to detennine and refine a crystal structure. In this work, the layer spacings of 6H SiC have been calculated and are within X-ray standard deviations. Under this premise, the layer spacings of 15R have been detennined. 29Si and 13C single crystal nmr studies of 6H SiC polytype indicate that all silicons and carbons are magnetically anisotropic. The relationship between a magnetic shielding tensor component and layer spacings has been derived. The comparisons between experimental and semi-empirical chemical shielding tensor components indicate that the paramagnetic shielding of silicon should be included in the single crystal chemical shift calculation.
Resumo:
Impurity free eluission spectra of HCCCHO and DCCCHO have been rephotographed using the electronic-energy-exchange method with benzene as a carrier gas. The near ultraviolet spectra of ReeCHO and DCCCHO were photographed in a sorption under conditions of high resolution with absorption path lengths up to 100 meters. The emission and absorption spectra of Propynal resulting from 3 n 1 t 1\ - A excitation has been reanalyzed in som.e detail. Botrl of the eH out-of-plane wagging modes were found to have negative anharmonicity. A barrier height of 56.8/0.0 cm- 1 and a nonplanar oft , , equilibrium angle of 17 3 /30 are calculated for the V 10/ lJ 11 modes. The in-plane and out-of-plane v1. brational modes in the 3A." and 1a~. ' elec ronic states of Propynal were subjected to a normal coordinate treatment in the approximat :on of tIle Urey-Bradley force field. From the relative oscillator strengths of the trans1·t1·0ns connect i ng t he v ibrat1•0n1ess lA' , state and t,he V1· bron1·C 3· if levels of the A state, the differences in equilibrium configuration were evaluated from an approximate Franck-Condon analysis based on the ground state normal coordinates. As this treatment gave 512 possible geometrical structures for the upper state, it 4 was necessary to resort to a comparison of the observed and calculated moments of inertia along with chemical intuition to isolate the structure. A test of the correctness of the calculated structure change and the vibrational assignment was raade by evaluating the intensities of the inplane and out-oi-plane fundarnental, sequence, and cross sequellce transitions y the exact Franck-Condon method.
Resumo:
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.
Resumo:
The relationships between vine water status, soil texture, and vine size were observed in four Niagara, Ontario Pinot noir vineyards in 2008 and 2009. The vineyards were divided into water status zones using geographic information systems (GIS) software to map the seasonal mean midday leaf water potential (,P), and dormant pruning shoot weights following the 2008 season. Fruit was harvested from all sentinel vines, bulked by water status zones and made into wine. Sensory analysis included a multidimensional sorting (MDS) task and descriptive analysis (DA) of the 2008 wines. Airborne multispectral images, with a spatial resolution of 38 cm, were captured four times in 2008 and three times in 2009, with the final flights around veraison. A semi-automatic process was developed to extract NDVI from the images, and a masking procedure was identified to create a vine-only NDVI image. 2008 and 2009 were cooler and wetter than mean years, and the range of water status zones was narrow. Yield per vine, vine size, anthocyanins and phenols were the least consistent variables. Divided by water status or vine size, there were no variables with differences between zones in all four vineyards in either year. Wines were not different between water status zones in any chemical analysis, and HPLC revealed that there were no differences in individual anthocyanins or phenolic compounds between water status zones within the vineyard sites. There were some notable correlations between vineyard and grape composition variables, and spatial trends were observed to be qualitatively related for many of the variables. The MDS task revealed that wines from each vineyard were more affected by random fermentation effects than water status effects. This was confirmed by the DA; there were no differences between wines from the water status zones within vineyard sites for any attribute. Remotely sensed NDVI (normalized difference vegetation index) correlated reasonably well with a number of grape composition variables, as well as soil type. Resampling to a lower spatial resolution did not appreciably affect the strength of correlations, and corresponded to the information contained in the masked images, while maintaining the range of values of NDVI. This study showed that in cool climates, there is the potential for using precision viticulture techniques to understand the variability in vineyards, but the variable weather presents a challenge for understanding the driving forces of that variability.