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.

The role of selection in functional explanations

In this essay I will argue that natural selection is more important to functional explanations than what has been thought in some of the literature in philosophy of biology. I start by giving a brief overview of the two paradigms cases of functional explanations: etiological functions and causal-role functions. i then consider one particular attempt to conciliate both perspectives given by David Buller (1998). Buller's trial to conciliate both etiological functions and causal-role functions results in what he calls a weak etiological theory. I argue that Buller has not succeeded in his construal of the weak etiological theory: he underestimates the role that selective processes have in functional explanations and so his theory may not be classified as an etiologial theory. As an alternative, I consider the account of etiological functions given by Ruth Millikan (1984) and I argue that Millikan's theory is more comprehensive to assess contentious case in biology like exaptations. Finally, I conclude by analyzing where the adoption of Millikan's theory leave us. I argue, contrary to Millikan and others, that once we assume the importance of natural selection in functional explanations, there is no strong reason to resist a linguistic reform of the word function and hence that the attempts to conciliate both etiological functions and causal-role functions are misplaced.

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.

Understanding the Racial Nature of Police and Immigrant Relations In Finland. The Case of Africans in Turku

The focus of this study is to examine the role of police and immigrants’ relations, as less is known about this process in the country. The studies were approached in two different ways. Firstly, an attempt was made to examine how immigrants view their encounters with the police. Secondly, the studies explored how aware the police are of immigrants’ experiences in their various encounters and interactions on the street level. An ancillary aim of the studies is to clarify, analyse and discuss how prejudice and stereotypes can be tackled, thereby contributing to the general debate about racism and discrimination for better ethnic relations in the country. The data in which this analysis was based is on a group of adults (n=88) from the total of 120 Africans questioned for the entire study (n=45) police cadets and (n=6) serving police officers from Turku. The present thesis is a compilation of five articles. A summary of each article findings follows, as the same data was used in all five studies. In the first study, a theoretical model was developed to examine the perceived knowledge of bias by immigrants resulting from race, culture and belief. This was also an attempt to explore whether this knowledge was predetermined in my attempt to classify and discuss as well as analyse the factors that may be influencing immigrants’ allegations of unfair treatment by the police in Turku. The main finding shows that in the first paper there was ignorance and naivety on the part of the police in their attitudes towards the African immigrant’s prior experiences with the police, and this may probably have resulted from stereotypes or their lack of experience as well as prior training with immigrants where these kinds of experience are rampant in the country (Egharevba, 2003 and 2004a). In exploring what leads to stereotypes, a working definition is the assumption that is prevalent among some segments of the population, including the police, that Finland is a homogenous country by employing certain conducts and behaviour towards ethnic and immigrant groups in the country. This to my understanding is stereotype. Historically this was true, but today the social topography of the country is changing and becoming even more complex. It is true that, on linguistic grounds, the country is multilingual, as there are a few recognised national minority languages (Swedish, Sami and Russian) as well as a number of immigrant languages including English. Apparently it is vital for the police to have a line of communication open when addressing the problem associated with immigrants in the country. The second paper moved a step further by examining African immigrants’ understanding of human rights as well as what human rights violation means or entails in their views as a result of their experiences with the police, both in Finland and in their country of origin. This approach became essential during the course of the study, especially when the participants were completing the questionnaire (N=88), where volunteers were solicited for a later date for an in-depth interview with the author. Many of the respondents came from countries where human rights are not well protected and seldom discussed publicly, therefore understanding their views on the subject can help to explain why some of the immigrants are sceptical about coming forward to report cases of batteries and assaults to the police, or even their experiences of being monitored in shopping malls in their new home and the reason behind their low level of trust in public authorities in Finland. The study showed that knowledge of human rights is notably low among some of the participants. The study also found that female respondents were less aware of human rights when compared with their male counterparts. This has resulted in some of the male participants focussing more on their traditional ways of thinking by not realising that they are in a new country where there is equality in sexes and lack of respect on gender terms is not condoned. The third paper focussed on the respondents’ experiences with the police in Turku and tried to explore police attitudes towards African immigrant clients, in addition to the role stereotype plays in police views of different cultures and how these views have impacted on immigrants’ views of discriminatory policing in Turku. The data is the same throughout the entire studies (n=88), except that some few participants were interviewed for the third paper thirty-five persons. The results showed that there is some bias in mass-media reports on the immigrants’ issues, due to selective portrayal of biases without much investigation being carried out before jumping to conclusions, especially when the issues at stake involve an immigrant (Egharevba, 2005a; Egharevba, 2004a and 2004b). In this vein, there was an allegation that the police are even biased while investigating cases of theft, especially if the stolen property is owned by an immigrant (Egharevba, 2006a, Egharevba, 2006b). One vital observation from the respondents’ various comments was that race has meaning in their encounters and interaction with the police in the country. This result led the author to conclude that the relation between the police and immigrants is still a challenge, as there is rampant fear and distrust towards the police by some segments of the participating respondents in the study. In the fourth paper the focus was on examining the respondents’ view of the police, with special emphasis on race and culture as well as the respondents’ perspective on police behaviour in Turku. This is because race, as it was relayed to me in the study, is a significant predictor of police perception (Egharevba, 2005a; Egharevba and Hannikianen, 2005). It is a known scientific fact that inter-group racial attitudes are the representation of group competition and perceived threat to power and status (Group-position theory). According to Blumer (1958) a sense of group threat is an essential element for the emergence of racial prejudice. Consequently, it was essential that we explored the existing relationship between the respondents and the police in order to have an understanding of this concept. The result indicates some local and international contextual issues and assumptions that were of importance tackling prejudice and discrimination as it exists within the police in the country. Moreover, we have to also remember that, for years, many of these African immigrants have been on the receiving end of unjust law enforcement in their various countries of origin, which has resulted in many of them feeling inferior and distrustful of the police even in their own country of origin. While discussing the issues of cultural difference and how it affects policing, we must also keep in mind the socio-cultural background of the participants, their level of language proficiency and educational background. The research data analysed in this study also confirmed the difficulties associated with cultural misunderstandings in interpreting issues and how these misunderstandings have affected police and immigrant relations in Finland. Finally, the fifth paper focussed on cadets’ attitudes towards African immigrants as well as serving police officers’ interaction with African clients. Secondly, the police level of awareness of African immigrants’ distrustfulness of their profession was unclear. For this reason, my questions in this fifth study examined the experiences and attitudes of police cadets and serving police officers as well as those of African immigrants in understanding how to improve this relationship in the country. The data was based on (n=88) immigrant participants, (n=45) police cadets and 6 serving police officers from the Turku police department. The result suggests that there is distrust of the police in the respondents’ interaction; this tends to have galvanised a heightened tension resulting from the lack of language proficiency (Egharevba and White, 2007; Egharevba and Hannikainen, 2005, and Egharevba, 2006b) The result also shows that the allegation of immigrants as being belittled by the police stems from the misconceptions of both parties as well as the notion of stop and search by the police in Turku. All these factors were observed to have contributed to the alleged police evasiveness and the lack of regular contact between the respondents and the police in their dealings. In other words, the police have only had job-related contact with many of the participants in the present study. The results also demonstrated the complexities caused by the low level of education among some of the African immigrants in their understanding about the Finnish culture, norms and values in the country. Thus, the framework constructed in these studies embodies diversity in national culture as well as the need for a further research study with a greater number of respondents (both from the police and immigrant/majority groups), in order to explore the different role cultures play in immigrant and majority citizens’ understanding of police work.

A contact-linguistic view on Finland-Swedish quotatives vara ’be’ and att ’that’

Artikel i konferensrapport.