Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH3SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH3, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.

Leibniz's theory of bodies: monadic aggregates, phenomena, or both?

Leibniz's conception of bodies seems to be a puzzling theory. Bodies are seen as aggregates of monads and as wellfounded phenomena. This has initiated controversy and unending discussions. The paper attempts to resolve the apparent inconsistencies by a new and formally spirited reconstruction of Leibniz's theory of monads and perception, on the one hand, and a (re-)formulation and precisation of his concept of preestablished harmony, on the other hand. Preestablished harmony is modelled basically as a covariation between the monadic and the ideal realm.

Benjamin's conception of language and Adorno's aesthetic theory

According to the theory of language of the young Benjamin, the primary task of language isn't the communication of contents, but to express itself as a "spiritual essence" in which also men take part. That conception according to which language would be a medium to signification of something outside it leads to a necessary decrease of its original strength and is thus denominated by Benjamin bürgerlich. The names of human language are remainders of an archaic state, in which things weren't yet mute and had their own language. Benjamin suggests also that all the arts remind the original language of things, as they make objects "speak" in form of sounds, colors, shapes etc. That relationship between arts as reminders of the "language of things" and the possible reconciliation of mankind with itself and with nature has been developed by Theodor Adorno in several of his writings, specially in the Aesthetic Theory, where the artwork is ultimately conceived as a construct pervaded by "language" in the widest meaning - not in the "bourgeois" sense.

THE FORMAL AND THE FORMALIZED: THE CASES OF SYLLOGISTIC AND SUPPOSITION THEORY

As a discipline, logic is arguably constituted of two main sub-projects: formal theories of argument validity on the basis of a small number of patterns, and theories of how to reduce the multiplicity of arguments in non-logical, informal contexts to the small number of patterns whose validity is systematically studied (i.e. theories of formalization). Regrettably, we now tend to view logic 'proper' exclusively as what falls under the first sub-project, to the neglect of the second, equally important sub-project. In this paper, I discuss two historical theories of argument formalization: Aristotle's syllogistic theory as presented in the "Prior Analytics", and medieval theories of supposition. They both illustrate this two-fold nature of logic, containing in particular illuminating reflections on how to formalize arguments (i.e. the second sub-project). In both cases, the formal methods employed differ from the usual modern technique of translating an argument in ordinary language into a specially designed symbolism, a formal language. The upshot is thus a plea for a broader conceptualization of what it means to formalize.

Rebuilding Defenses: Explorations in Norman Fairclough’s Theory of Critical Discourse Analysis

Tutkielmassa eritellään Norman Faircloughin kriittisen diskurssianalyysin teoriaa ja siihen kohdistettua kritiikkiä. Pyrkimyksenä on sovittaa näitä erilaisia näkemyksiä keskenään ja tarjota ratkaisuja yhteen kiriittisen diskurssianalyysin keskeiseen ongelmaan eli emansipaation (sosiaalisten epäkohtien tunnistamisen ja ratkaisemisen) puutteellisuuteen. Teoriaosuudesta esiin nousevia mahdollisuuksia sovelletaan tekstianalyysiin. Tutkimuksen kohteena on teksti Rebuilding America’s Defenses: Strategy, Forces and Resources For a New Century ja jossain määrin sen tuottanut järjestö Project for the New American Century. Näitä tarkastellaan ennen kaikkea sosiaalisina ilmiöinä ja suhteessa toisiinsa. Faircloughin mallin suurimmiksi ongelmiksi muodostuvat perinteinen käsitys kielestä, jonka mukaan kielen järjestelmän abstraktit ja sisäiset suhteet ovat tärkeimpiä, sekä ideologinen vastakkainasettelu kritiikin lähtökohtana. Ensimmäinen johtaa kielellisten tutkimustulosten epätyydyttävään kykyyn selittää sosiaalisia havaintoja ja jälkimmäinen poliittiseen tai maailmankatsomukselliseen väittelyyn, joka ei mahdollista uusia näkemyksiä. Tutkielman lopputulema on, että keskittymällä asiasisältöön kielen rakenteen sijasta ja ymmärtämällä tekstin tuottaja yksittäisenä, rajattuna sosiaalisena toimijana voidaan analyysiin saada avoimuutta ja täsmällisyyttä. Kriittiinen diskurssianalyysi kaipaa tällaista näkemystä kielellisten analyysien tueksi ja uudenlaisen relevanssin löytääkseen.

Causation and dominance : a study of Finnish causative verbs expressing social dominance

En väsentlig fråga inom såväl lingvistiska som kognitiva teorier är, hur språket beskriver kausala relationer. I finskan finns det en speciell typ av kausativa verb avledda med suffixet (U)ttA som används för att uttrycka att handlingen i fråga utförs av någon annan än subjektreferenten, t.ex. Maija haetuttaa Matilla kirjastosta kirjan ’Maija låter Matti hämta boken från biblioteket’ och Matti juoksuttaa Maijan kaupunkiin ’Matti låter Maija springa till staden’. Syftet med denna avhandling var att med exempel av sociala dominansens kausativer undersöka ordbildningens natur samt begreppet ’socialt förorsakande’. För att beskriva avledningars regelbundna argumentstruktur i form av kopplingen mellan syntaxen och semantiken upprättades deras prototypiska strukturer. Dessa verb har emellertid också specifika användningsområden som framhäver variationer i sociala relationer. Säregna egenskaper hos den sociala dominansens kausativer inkluderades i undersökningen och definierades som konstruktioner. Konstruktionerna omfattar speciella syntaktiska och/eller semantiska element och utöver det också pragmatiska värderande implikationer. Uppbyggnaden av den sociala dimensionen hos de undersökta verben består av egenskaper förbundna med typen av förorsakande, argumentens agentiva egenskaper (aktivitet eller passivitet, dominans, kontroll, viljestyrdhet och ansvarighet) samt konventionaliserade attityder och tolkningar. Ett exempel på en s.k. 'tolkningskonstruktion’ är den negativa dominansens uttryck som i avhandlingen kallas Maktmissbrukskonstruktionen. Denna konstruktion inkluderar talarens starkt kritiska hållning till den uttryckta situationen, t.ex. Asiakas juoksuttaa lentoemäntää ’Kunden låter flygvärdinnan springa’. Dessa konstruktioner fyller en viktig funktion i språklig kommunikation: att beskriva avvikande av sociala normer och att foga expressivitet till budskapet. Metodologiskt kombinerar denna avhandling teorier som baseras på det aktuella språkbruket och teoretisk lingvistisk analys. Verbens samt konstruktionernas konceptuella lexikala struktur och prototypstrukturerna analyserades med hjälp av den konceptuella semantikens verktyg, som har utvecklats av Jackendoff, Nikanne och Pörn.

Remarks on abstract Galois theory

This paper is a historical companion to a previous one, in which it was studied the so-called abstract Galois theory as formulated by the Portuguese mathematician José Sebastião e Silva (see da Costa, Rodrigues (2007)). Our purpose is to present some applications of abstract Galois theory to higher-order model theory, to discuss Silva's notion of expressibility and to outline a classical Galois theory that can be obtained inside the two versions of the abstract theory, those of Mark Krasner and of Silva. Some comments are made on the universal theory of (set-theoretic) structures.

The relation between the general maxim of causality and the principle of uniformity in hume's theory of knowledge

ABSTRACT When Hume, in the Treatise on Human Nature, began his examination of the relation of cause and effect, in particular, of the idea of necessary connection which is its essential constituent, he identified two preliminary questions that should guide his research: (1) For what reason we pronounce it necessary that every thing whose existence has a beginning should also have a cause and (2) Why we conclude that such particular causes must necessarily have such particular effects? (1.3.2, 14-15) Hume observes that our belief in these principles can result neither from an intuitive grasp of their truth nor from a reasoning that could establish them by demonstrative means. In particular, with respect to the first, Hume examines and rejects some arguments with which Locke, Hobbes and Clarke tried to demonstrate it, and suggests, by exclusion, that the belief that we place on it can only come from experience. Somewhat surprisingly, however, Hume does not proceed to show how that derivation of experience could be made, but proposes instead to move directly to an examination of the second principle, saying that, "perhaps, be found in the end, that the same answer will serve for both questions" (1.3.3, 9). Hume's answer to the second question is well known, but the first question is never answered in the rest of the Treatise, and it is even doubtful that it could be, which would explain why Hume has simply chosen to remove any mention of it when he recompiled his theses on causation in the Enquiry concerning Human Understanding. Given this situation, an interesting question that naturally arises is to investigate the relations of logical or conceptual implication between these two principles. Hume seems to have thought that an answer to (2) would also be sufficient to provide an answer to (1). Henry Allison, in his turn, argued (in Custom and Reason in Hume, p. 94-97) that the two questions are logically independent. My proposal here is to try to show that there is indeed a logical dependency between them, but the implication is, rather, from (1) to (2). If accepted, this result may be particularly interesting for an interpretation of the scope of the so-called "Kant's reply to Hume" in the Second Analogy of Experience, which is structured as a proof of the a priori character of (1), but whose implications for (2) remain controversial.

The notion of process in nonstandard theory and in Whiteheadian metaphysics

In this article I intend to show that certain aspects of A.N. Whitehead's philosophy of organism and especially his epochal theory of time, as mainly exposed in his well-known work Process and Reality, can serve in clarify the underlying assumptions that shape nonstandard mathematical theories as such and also as metatheories of quantum mechanics. Concerning the latter issue, I point to an already significant research on nonstandard versions of quantum mechanics; two of these approaches are chosen to be critically presented in relation to the scope of this work. The main point of the paper is that, insofar as we can refer a nonstandard mathematical entity to a kind of axiomatical formalization essentially 'codifying' an underlying mental process indescribable as such by analytic means, we can possibly apply certain principles of Whitehead's metaphysical scheme focused on the key notion of process which is generally conceived as the becoming of actual entities. This is done in the sense of a unifying approach to provide an interpretation of nonstandard mathematical theories as such and also, in their metatheoretical status, as a formalization of the empirical-experimental context of quantum mechanics.

Quasiconformal mappings and inequalities involving special functions

This PhD thesis in Mathematics belongs to the field of Geometric Function Theory. The thesis consists of four original papers. The topic studied deals with quasiconformal mappings and their distortion theory in Euclidean n-dimensional spaces. This theory has its roots in the pioneering papers of F. W. Gehring and J. Väisälä published in the early 1960’s and it has been studied by many mathematicians thereafter. In the first paper we refine the known bounds for the so-called Mori constant and also estimate the distortion in the hyperbolic metric. The second paper deals with radial functions which are simple examples of quasiconformal mappings. These radial functions lead us to the study of the so-called p-angular distance which has been studied recently e.g. by L. Maligranda and S. Dragomir. In the third paper we study a class of functions of a real variable studied by P. Lindqvist in an influential paper. This leads one to study parametrized analogues of classical trigonometric and hyperbolic functions which for the parameter value p = 2 coincide with the classical functions. Gaussian hypergeometric functions have an important role in the study of these special functions. Several new inequalities and identities involving p-analogues of these functions are also given. In the fourth paper we study the generalized complete elliptic integrals, modular functions and some related functions. We find the upper and lower bounds of these functions, and those bounds are given in a simple form. This theory has a long history which goes back two centuries and includes names such as A. M. Legendre, C. Jacobi, C. F. Gauss. Modular functions also occur in the study of quasiconformal mappings. Conformal invariants, such as the modulus of a curve family, are often applied in quasiconformal mapping theory. The invariants can be sometimes expressed in terms of special conformal mappings. This fact explains why special functions often occur in this theory.

Charge transport in disordered materials : simulations, theory, and numerical modeling of hopping transport and electron-hole recombination

Min avhandling behandlar hur oordnade material leder elektrisk ström. Bland materialen som studeras finns ledande polymerer, d.v.s. plaster som leder ström, och mer allmänt organiska halvledare. Av de här materialen har man kunnat bygga elektroniska komponenter, och man hoppas på att kunna trycka hela kretsar av organiska material. För de här tillämpningarna är det viktigt att förstå hur materialen själva leder elektrisk ström. Termen oordnade material syftar på material som saknar kristallstruktur. Oordningen gör att elektronernas tillstånd blir lokaliserade i rummet, så att en elektron i ett visst tillstånd är begränsad t.ex. till en molekyl eller ett segment av en polymer. Det här kan jämföras med kristallina material, där ett elektrontillstånd är utspritt över hela kristallen (men i stället har en väldefinierad rörelsemängd). Elektronerna (eller hålen) i det oordnade materialet kan röra sig genom att tunnelera mellan de lokaliserade tillstånden. Utgående från egenskaperna för den här tunneleringsprocessen, kan man bestämma transportegenskaperna för hela materialet. Det här är utgångspunkten för den så kallade hopptransportmodellen, som jag har använt mig av. Hopptransportmodellen innehåller flera drastiska förenklingar. Till exempel betraktas elektrontillstånden som punktformiga, så att tunneleringssannolikheten mellan två tillstånd endast beror på avståndet mellan dem, och inte på deras relativa orientation. En annan förenkling är att behandla det kvantmekaniska tunneleringsproblemet som en klassisk process, en slumpvandring. Trots de här grova approximationerna visar hopptransportmodellen ändå många av de fenomen som uppträder i de verkliga materialen som man vill modellera. Man kan kanske säga att hopptransportmodellen är den enklaste modell för oordnade material som fortfarande är intressant att studera. Man har inte hittat exakta analytiska lösningar för hopptransportmodellen, därför använder man approximationer och numeriska metoder, ofta i form av datorberäkningar. Vi har använt både analytiska metoder och numeriska beräkningar för att studera olika aspekter av hopptransportmodellen. En viktig del av artiklarna som min avhandling baserar sig på är att jämföra analytiska och numeriska resultat. Min andel av arbetet har främst varit att utveckla de numeriska metoderna och applicera dem på hopptransportmodellen. Därför fokuserar jag på den här delen av arbetet i avhandlingens introduktionsdel. Ett sätt att studera hopptransportmodellen numeriskt är att direkt utföra en slumpvandringsprocess med ett datorprogram. Genom att föra statisik över slumpvandringen kan man beräkna olika transportegenskaper i modellen. Det här är en så kallad Monte Carlo-metod, eftersom själva beräkningen är en slumpmässig process. I stället för att följa rörelsebanan för enskilda elektroner, kan man beräkna sannolikheten vid jämvikt för att hitta en elektron i olika tillstånd. Man ställer upp ett system av ekvationer, som relaterar sannolikheterna för att hitta elektronen i olika tillstånd i systemet med flödet, strömmen, mellan de olika tillstånden. Genom att lösa ekvationssystemet fås sannolikhetsfördelningen för elektronerna. Från sannolikhetsfördelningen kan sedan strömmen och materialets transportegenskaper beräknas. En aspekt av hopptransportmodellen som vi studerat är elektronernas diffusion, d.v.s. deras slumpmässiga rörelse. Om man betraktar en samling elektroner, så sprider den med tiden ut sig över ett större område. Det är känt att diffusionshastigheten beror av elfältet, så att elektronerna sprider sig fortare om de påverkas av ett elektriskt fält. Vi har undersökt den här processen, och visat att beteendet är väldigt olika i endimensionella system, jämfört med två- och tredimensionella. I två och tre dimensioner beror diffusionskoefficienten kvadratiskt av elfältet, medan beroendet i en dimension är linjärt. En annan aspekt vi studerat är negativ differentiell konduktivitet, d.v.s. att strömmen i ett material minskar då man ökar spänningen över det. Eftersom det här fenomenet har uppmätts i organiska minnesceller, ville vi undersöka om fenomenet också kan uppstå i hopptransportmodellen. Det visade sig att det i modellen finns två olika mekanismer som kan ge upphov till negativ differentiell konduktivitet. Dels kan elektronerna fastna i fällor, återvändsgränder i systemet, som är sådana att det är svårare att ta sig ur dem då elfältet är stort. Då kan elektronernas medelhastighet och därmed strömmen i materialet minska med ökande elfält. Elektrisk växelverkan mellan elektronerna kan också leda till samma beteende, genom en så kallad coulombblockad. En coulombblockad kan uppstå om antalet ledningselektroner i materialet ökar med ökande spänning. Elektronerna repellerar varandra och ett större antal elektroner kan leda till att transporten blir långsammare, d.v.s. att strömmen minskar.

Reagan's mythical America : towards a narrative theory of prophetic politics

Lectio praecursoria Tampereen yliopistossa 17.8.2010.

Desenvolvimento e testes de uma semeadora-adubadora modular para pequenas propriedades rurais

O trabalho apresenta o desenvolvimento e testes de campo de equipamento agrícola modular. Para o desenvolvimento do equipamento, foi utilizada metodologia de projeto para sistemas modulares. O objetivo principal foi desenvolver um sistema modular que contribuísse para melhorar o atual quadro de mecanização agrícola da pequena propriedade rural, enfocando alguns dos equipamentos destinados às atividades conservacionistas de cultivo. Por ser modular, o equipamento atende às funções de semear-adubar, escarificar e sulcar o solo. Para a função semear-adubar, podem ser usados cinzéis e disco duplo para a semeadura; já para as funções de escarificação e sulcagem, podem ser usadas ferramentas específicas, facilmente intercambiadas em um chassi tubular principal. Os resultados para solo argiloso (Typic Oxisols), com umidade em torno de 20,5% e massa seca de 11,5 t ha-1 para a variante semeadora-adubadora com duplo cinzel, foram satisfatórios com relação aos parâmetros de patinagem das rodas motoras, regularidade de distribuição em profundidade, cobertura das sementes, distribuição longitudinal das sementes e emergência de plantas.

Frequency-Domain and Wide-Pulse Time-Domain Measurements of Lanthanide Luminescence and Lanthanide-Based Resonance Energy Transfer

Resonance energy transfer (RET) is a non-radiative transfer of the excitation energy from the initially excited luminescent donor to an acceptor. The requirements for the resonance energy transfer are: i) the spectral overlap between the donor emission spectrum and the acceptor absorption spectrum, ii) the close proximity of the donor and the acceptor, and iii) the suitable relative orientations of the donor emission and the acceptor absorption transition dipoles. As a result of the RET process the donor luminescence intensity and the donor lifetime are decreased. If the acceptor is luminescent, a sensitized acceptor emission appears. The rate of RET depends strongly on the donor–acceptor distance (r) and is inversely proportional to r6. The distance dependence of RET is utilized in binding assays. The proximity requirement and the selective detection of the RET-modified emission signal allow homogeneous separation free assays. The term lanthanide-based RET is used when luminescent lanthanide compounds are used as donors. The long luminescence lifetimes, the large Stokes’ shifts and the intense, sharply-spiked emission spectra of the lanthanide donors offer advantages over the conventional organic donor molecules. Both the organic lanthanide chelates and the inorganic up-converting phosphor (UCP) particles have been used as donor labels in the RET based binding assays. In the present work lanthanide luminescence and lanthanide-based resonance energy transfer phenomena were studied. Luminescence lifetime measurements had an essential role in the research. Modular frequency-domain and time-domain luminometers were assembled and used successfully in the lifetime measurements. The frequency-domain luminometer operated in the low frequency domain ( 100 kHz) and utilized a novel dual-phase lock-in detection of the luminescence. One of the studied phenomena was the recently discovered non-overlapping fluorescence resonance energy transfer (nFRET). The studied properties were the distance and temperature dependences of nFRET. The distance dependence was found to deviate from the Förster theory and a clear temperature dependence was observed whereas conventional RET was completely independent of the temperature. Based on the experimental results two thermally activated mechanisms were proposed for the nFRET process. The work with the UCP particles involved the measurement of the luminescence properties of the UCP particles synthesized in our laboratory. The goal of the UCP particle research is to develop UCP donor labels for binding assays. In the present work the effect of the dopant concentrations and the core–shell structure on the total up-conversion luminescence intensity, the red–green emission ratio, and the luminescence lifetime was studied. Also the non-radiative nature of the energy transfer from the UCP particle donors to organic acceptors was demonstrated for the first time in aqueous environment and with a controlled donor–acceptor distance.