A brief introduction to molecular orbital theory of simple polyatomic molecules for undergraduate chemistry students

A simple, four-step method for better introducing undergraduate students to the fundamentals of molecular orbital (MO) theory of the polyatomic molecules H2O, NH3, BH3 and SiH4 using group theory is reported. These molecules serve to illustrate the concept of ligand group orbitals (LGOs) and subsequent construction of MO energy diagrams on the basis of molecular symmetry requirements.

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.

Molecular modeling of asymmetric induction in heterogeneously catalyzed hydrogenation of the C=O bond

Modifiering av metallytor med starkt adsorberade kirala organiska molekyler är eventuellt den mest relevanta teknik man vet i dag för att skapa kirala ytor. Den kan utnyttjas i katalytisk produktion av enantiomeriskt rena kirala föreningar som behövs t.ex. som läkemedel och aromkemikalier. Trots många fördelar av asymmetrisk heterogen katalys jämfört med andra sätt för att få kirala föreningar, har den ändå inte blivit ett allmänt verktyg för storskaliga tillämpningar. Detta beror t.ex. på brist på djupare kunskaper i katalytiska reaktionsmekanismer och ursprunget för asymmetrisk induktion. I denna studie användes molekylmodelleringstekniker för att studera asymmetriska, heterogena katalytiska system, speciellt hydrering av prokirala karbonylföreningar till motsvarande kirala alkoholer på cinchona-alkaloidmodifierade Pt-katalysatorer. 1-Fenyl-1,2-propandion (PPD) och några andra föreningar, som innehåller en prokiral C=O-grupp, användes som reaktanter. Konformationer av reaktanter och cinchona-alkaloider (som kallas modifierare) samt vätebundna 1:1-komplex mellan dem studerades i gas- och lösningsfas med metoder som baserar sig på vågfunktionsteori och täthetsfunktionalteori (DFT). För beräkningen av protonaffiniteter användes också högst noggranna kombinationsmetoder såsom G2(MP2). Den relativa populationen av modifierarnas konformationer varierade som funktion av modifieraren, dess protonering och lösningsmedlet. Flera reaktant–modifierareinteraktionsgeometrier beaktades. Slutsatserna på riktning av stereoselektivitet baserade sig på den relativa termodynamiska stabiliteten av de diastereomeriska reaktant–modifierare-komplexen samt energierna hos π- och π*-orbitalerna i den reaktiva karbonylgruppen. Adsorption och reaktioner på Pt(111)-ytan betraktades med DFT. Regioselektivitet i hydreringen av PPD och 2,3-hexandion kunde förklaras med molekyl–yta-interaktioner. Storleken och formen av klustret använt för att beskriva Pt-ytan inverkade inte bara på adsorptionsenergierna utan också på de relativa stabiliteterna av olika adsorptionsstrukturer av en molekyl. Populationerna av modifierarnas konformationer i gas- och lösningsfas korrelerade inte med populationerna på Pt-ytan eller med enantioselektiviteten i hydreringen av PPD på Pt–cinchona-katalysatorer. Vissa modifierares konformationer och reaktant–modifierare-interaktionsgeometrier var stabila bara på metallytan. Teoretiskt beräknade potentialenergiprofiler för hydrering av kirala α-hydroxiketoner på Pt implicerade preferens för parvis additionsmekanism för väte och selektiviteter i harmoni med experimenten. De uppnådda resultaten ökar uppfattningen om kirala heterogena katalytiska system och kunde därför utnyttjas i utvecklingen av nya, mera aktiva och selektiva kirala katalysatorer.

Tilirahan arvostaminen, korkoriskin hallinta ja Suomen talletusmarkkinat

Tilirahalla tarkoitetaan matalan koron tilejä, joihin liittyy tallettajan optio nostaa talletus haluamanaan ajankohtana. Tästä huolimatta tilirahan on havaittu olevan pankille kohtalaisen pysyvää rahoitusta. Pitkä keskimääräinen elinikä yhdistettynä matalaan kustannukseen tekee tilirahasta yhden pankin merkittävimmistä tulonlähteistä. Suuri korkomarginaali ja talletuskoron jäykkyys suhteessa markkinakorkotasoon aiheuttavat puolestaan pankille suuren korkoriskin. Tutkielma vastaa kysymykseen mitä tekijöitä tulee ottaa huomioon tilirahan arvostamisessa ja korkoriskin hallinnassa Suomen talletusmarkkinoilla. Kirjallisuuskatsauksessa esitettyjä tietoja ja niiden soveltuvuutta suomalaisten kotitalouksien tilirahavolyymien kehityksen ennustamisessa arvioidaan lopuksi Suomen Pankista, Eurostatista ja Tilastokeskuksesta saatavien lukujen pohjilta. Virallisista tilastoista johdettujen arvioiden havaittiin osin poikkeavan kirjallisuuskatsauksessa esitetystä. Syynä tähän nähdään eri maiden väliset erot kotitalouksien säästämiskäyttäytymisessä. Suomessa kotitalouksien käyttäytymistä ei näytä ensisijaisesti ohjaavan taloudelliset vaan ei-taloudelliset tekijät kuten parempi likviditeetti. Lisäksi bruttokansantuotteen ja tilirahavolyymin kehityksen välillä havaittiin Suomessa todennäköinen korrelaatio. Alueelliset erot tuleekin huomioida aikaisempia tutkimustuloksia hyödynnettäessä.

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.

DISAGREEING OVER EVALUATIVES: PREFERENCE, NORMATIVE AND MORAL DISCOURSE

Abstract Why would we argue about taste, norms or morality when we know that these topics are relative to taste preferences, systems of norms or values to which we are committed? Yet, disagreements over these topics are common in our evaluative discourses. I will claim that the motives to discuss rely on our attitudes towards the standard held by the speakers in each domain of discourse, relating different attitudes to different motives -mainly, conviction and correction. These notions of attitudes and motives will allow me to claim that different domains of evaluative discourse have a different distribution of disagreements driven by them.