Theoretical Investigation on the Effect of Different Nitrogen Donors on Intramolecular Se center dot center dot center dot N Interactions

The effect of different donor nitrogen atoms on the strength and nature of intramolecular Se center dot center dot center dot N interactions is evaluated for organoselenium compounds having N,N-dimethylaminomethyl (dime), oxazoline (oxa) and pyridyl (py) substituents. Quantum chemical calculations on three series of compounds [2-(dime)C6H4SeX (1a-g), 2-(oxa)C6H4SeX (2a-g), 2- (py)C6H4SeX (3-ag); X=Cl, Br, OH, CN, SPh, SePh, CH3] at the B3LYP/6-31G(d) level show that the stability of different conformers depends on the strength of intramolecular nonbonded Se center dot center dot center dot N interactions. Natural bond orbital (NBO), NBO deletion and atoms in molecules (AIM) analyses suggest that the nature of the Se center dot center dot center dot N interaction is predominantly covalent and involves nN ->sigma*(Se-X) orbital interaction. In the three series of compounds, the strength of the Se center dot center dot center dot N interaction decreases in the order 3>2>1 for a particular X, and it decreases in the order Cl > Br > OH>SPh approximate to CN approximate to SePh>CH3 for all the three series 1-3. However, further analyses suggest that the differences in strength of Se center dot center dot center dot N interaction in 1-3 is predominantly determined by the distance between the Se and N atoms, which in turn is an outcome of specific structures of 1, 2 and 3, and the nature of the donor nitrogen atoms involved has very little effect on the strength of Se center dot center dot center dot N interaction. It is also observed that Se center dot center dot center dot N interaction becomes stronger in polar solvents such as CHCl3, as indicated by the shorter r(Se center dot center dot center dot N) and higher E-Se center dot center dot center dot N values in CHCl3 compared to those observed in the gas phase.

Theory of the unusual doping and temperature dependence of photoemission spectra in manganites

A recent, major, puzzle in the core-level photoemission spectra of doped manganites is the observation of a 1–2 eV wide shoulder with intensity varying with temperature T as the square of the magnetization over a T scale of order 200 K, an order of magnitude less than electronic energies. This is addressed and resolved here, by extending a recently proposed two-fluid polaron–mobile electron model for these systems to include core-hole effects. The position of the shoulder is found to be determined by Coulomb and Jahn-Teller energies, while its spectral weight is determined by the mobile electron energetics which is strongly T and doping dependent, due to annealed disorder scattering from the polarons and the t2g core spins. Our theory accounts quantitatively for the observed T dependence of the difference spectra, and furthermore, explains the observed correspondence between spectral changes due to increasing doping and decreasing T.

Simplified theory of optical nonlinearities in spin-polarized bulk GaAs

Apart from their intrinsic physical interest, spin-polarized many-body effects are expected to be important to the working of spintronic devices. A vast literature exists on the effects of a spin-unpolarized electron-hole plasma on the optical properties of a semiconductor. Here, we include the spin degree of freedom to model optical absorption of circularly polarized light by spin-polarized bulk GaAs. Our model is easy to implement and does not require elaborate numerics, since it is based on the closed-form analytical pair-equation formula that is valid in 3d. The efficacy of our approach is demonstrated by a comparison with recent experimental data.

Magnetic trapping of Yb in the metastable P-3(2) state

We report magnetic trapping of Yb in the excited P-3(2) state. This state, with a lifetime of 15 s, could play an important role in studies ranging from optical clocks and quantum computation to the search for a permanent electric dipole moment. Yb atoms are first cooled and trapped in the ground state in a 399-nm magneto-optic trap. The cold atoms are then pumped into the excited state by driving the S-1(0) -> P-3(1) -> S-3(1) transition. Atoms in the P-3(2) state are magnetically trapped in a spherical quadrupole field with an axial gradient of 110 G/cm. We trap up to 10(6) atoms with a lifetime of 1.5 s.

Simplified theory of optical nonlinearities in spin-polarized bulk GaAs

Apart from their intrinsic physical interest, spin-polarized many-body effects are expected to be important to the working of spintronic devices. A vast literature exists on the effects of a spin-unpolarized electron-hole plasma on the optical properties of a semiconductor. Here, we include the spin degree of freedom to model optical absorption of circularly polarized light by spin-polarized bulk GaAs. Our model is easy to implement and does not require elaborate numerics, since it is based on the closed-form analytical pair-equation formula that is valid in 3d. The efficacy of our approach is demonstrated by a comparison with recent experimental data.

Interculturality in Theory and Practice in the Master's Programme of Intercultural Bilingual Education in Bolivia

Tämän tutkielman aiheena on kulttuurienvälisyys kulttuurienvälisessä kaksikielisessä opetuksessa (Educación Intercultural Bilingüe, EIB) Boliviassa ja erityisesti kulttuurienvälisen kaksikielisen koulutuksen maisteriohjelmassa (Maestría en Educación Intercultural Bilingüe), jota koordinoi PROEIB Andes -järjestö yhteistyössä Cochabamban Universidad Mayor de San Simónin kanssa. Tutkielman tarkoituksena on selvittää, miten kulttuurienvälisyys määritellään ja mitä se käytännössä merkitsee opetuksen eri osa-alueilla: sisällöissä, opetusmetodeissa ja -materiaaleissa sekä arvioinnissa. Koska kulttuurienvälisen kaksikielisen opetuksen toteutus ja tutkiminen eri Latinalaisen Amerikan maissa on tähän asti painottunut lähes yksinomaan perusopetukseen, pyrin työssäni keskittymään kulttuurienvälisyyden ilmentymiin nimenomaan bolivialaisessa korkeakoulukontekstissa. Tutkielman aineistona on käytetty kahdeksaa EIB -asiantuntijoiden teemahaastattelua, jotka FM Eila Isotalus on tehnyt Boliviassa vuonna 2004. Haastatteluaineisto analysoitiin teoriasidonnaista eli abduktiivista sisällönanalyysiä käyttäen. Tutkielman teoriatausta koostuu yhtäältä kulttuurienvälisyyteen ja monikulttuurisuuteen liittyvien käsitteiden määrittelystä, ja toisaalta kulttuurienväliseen opetukseen liittyvien mallien esittelystä. Aineiston analyysissä avuksi on ollut etenkin James A. Banksin teoria monikulttuurisen opetuksen viidestä ulottuvuudesta, joiden kautta on voitu pohtia kulttuurienvälisyyden toteutumista opetuksen eri osa-alueilla ja nostaa esille bolivialaisen kulttuurienvälisen opetuksen erityispiirteitä. Aineiston analyysissä ilmenee, että kulttuurienvälisyyden käsitteen määrittely on vahvasti kontekstisidonnainen ja jatkuva prosessi, johon vaikuttavat eri toimijoiden näkemykset ja vaatimukset. EIB -asiantuntijoiden esittämät määrittelyt voidaan jakaa makro- ja mikrososiaaliseen kategoriaan sen mukaan, nähdäänkö kulttuurienvälisyys ensisijaisesti yhteiskunnallisena vai yksilötason käsitteenä. Aineistossa korostuu ajatus latinalaisamerikkalaisesta kulttuurienvälisyydestä poliittisena käsitteenä, jonka keskiössä on vaatimus yhteiskunnallisten valtasuhteiden muutoksesta. Yksi suurimmista haasteista kulttuurienvälisyyden toteuttamisessa bolivialaisessa korkeakouluopetuksessa ovat akateemiseen kulttuuriin liittyvät perinteet, jotka vaikeuttavat uusien toimintatapojen omaksumista. Kulttuurienvälisyys opetuksessa on toistaiseksi tarkoittanut etupäässä sisältöjen monipuolistamista lisäämällä opetusohjelmiin elementtejä paikallisista kulttuureista. Tärkeänä askeleena EIB:n kehityksessä voidaan pitää painopisteen siirtymistä sisältökysymyksistä kulttuurienvälisten opetusmetodien luomiseen. Näiden opetusmenetelmien tulisi pohjautua ymmärrykseen oppimisesta kokonaisvaltaisena, yhteisöllisenä prosessina ja siten kuroa umpeen kuilua koulun ja yhteisöjen arkielämän välillä. Opetusmenetelmien ja -materiaalien suhteen keskeinen kulttuurienvälisyyteen liittyvä kysymys on intiaanikansojen suullisen kulttuurin ja tiedon jakamisen perinteiden hyödyntäminen opetuksessa. Maisteriohjelman opiskelijoiden arvioinnissa pyritään huomioimaan yksilön kokonaisvaltainen kehitys pelkkien opintosuoritusten sijasta, mutta arvosanoihin pohjautuvasta arvostelukäytännöstä ei ole toistaiseksi voitu luopua yliopiston vaatimusten vuoksi. Kaiken kaikkiaan kulttuurienvälisyyden toteuttaminen EIB:ssä ja maisteriohjelmassa on pitkän tähtäimen prosessi, joka vaatii perinteisten opetuskäytäntöjen kyseenalaistamista ja korkeakouluopetuksessa myös akateemisen kulttuurin haastamista. On oleellisen tärkeää, että prosessiin osallistuvat asiantuntijoiden ohella myös esimerkiksi opiskelijat, intiaaniyhteisöt ja -järjestöaktiivit.

Influence of External Light Waves on the Thermoelectric Power Under Strong Magnetic Field in Ultrathin Films, Quantum Wires and Quantum Dots of Optoelectronic Materials

In this paper, an attempt is made to study the influence of external light waves on the thermoelectric power under strong magnetic field (TPSM) in ultrathin films (UFs), quantum wires (QWs) and quantum dots (QDs) of optoelectronic materials whose unperturbed dispersion relation of the conduction electrons are defined by three and two band models of Kane together with parabolic energy bands on the basis of newly formulated electron dispersion laws in each case. We have plotted the TPSM as functions of film thickness, electron concentration, light intensity and wavelength for UFs, QWs and ODs of InSb, GaAs, Hg1-xCdxTe and In1-xGaxAsyP1-y respectively. It appears from the figures that for UFs, the TPSM increases with increasing thickness in quantum steps, decreases with increasing electron degeneracy exhibiting entirely different types of oscillations and changes with both light intensity and wavelength and these two latter types of plots are the direct signature of light waves on opto-TPSM. For QWs, the opto-TPSM exhibits rectangular oscillations with increasing thickness and shows enhanced spiky oscillations with electron concentration per unit length. For QDs, the opto-TPSM increases with increasing film thickness exhibiting trapezoidal variations which occurs during quantum jumps and the length and breadth of the trapezoids are totally dependent on energy band constants. Under the condition of non-degeneracy, the results of opto-TPSM gets simplified into the well-known form of classical TPSM equation which the function of three constants only and being invariant of the signature of band structure.

Simplified theory of carrier back-scattering in semiconducting carbon nanotubes: A Kane's model approach

We present a simplified yet analytical formulation of the carrier backscattering coefficient for zig-zag semiconducting single walled carbon nanotubes under diffusive regime. The electron-phonon scattering rate for longitudinal acoustic, optical, and zone-boundary phonon emissions for both inter- and intrasubband transition rates have been derived using Kane's nonparabolic energy subband model.The expressions for the mean free path and diffusive resistance have been formulated incorporating the aforementioned phonon scattering. Appropriate overlap function in Fermi's golden rule has been incorporated for a more general approach. The effect of energy subbands on low and high bias zones for the onset of longitudinal acoustic, optical, and zone-boundary phonon emissions and absorption have been analytically addressed. 90% transmission of the carriers from the source to the drain at 400 K for a 5 mu m long nanotube at 105 V m(-1) has been exhibited. The analytical results are in good agreement with the available experimental data. (c) 2010 American Institute of Physics.

Polarographic and redox potential studies on copper(I) and copper(II) and their complexes. Part III. Copper (I and II)-ethylene diamine and edta complexes and theory of formation of step reduction waves in cupric copper systems

Polarographic and redox potential measurements on the cupric and cuprous complexes of ethylenediamine and EDTA have been carried out. From the ratio of the stability constants of the cupric and cuprous complexes, and the stability constant of the cupric complex, the stability constant of the cuprous-ethylenediamine complex is obtained. In the case of the EDTA complex it has been possible to obtain only βic/β2ous from the equilibrium concentrations of the cuprous and cupric complexes and the disproportionation constant. The inequalities for the appearance of step reduction waves have been given. The values of the stability constants of the cupric and cuprous complexes determined by the polarographic-redox potential method have been used to explain the appearance of step reduction waves in some systems and the non-appearance in other systems.

Experimental evidence of the cavity theory of sorption-desorption hysteresis by a study of the effect of electric discharge on entrapped water in silica gel

With the use of the quartz fiber spring balance, sorptions and desorptions of water on silica gel at 30°C were studied and the permanent and reproducible hysteresis loop was obtained. At different points on the desorption curve forming the loop, the gel was subjected to high tension glow electric discharge. As a result of the electric discharge, the gel at any point on the desorption curve shifts to a corresponding point on the sorption curve. This is due to the release from the cavities of gel of the entrapped water held in a metastable state. The electric discharge has no effect on the gel at different points on portions of the desorption curve which coincide with the sorption curve and also on the sorption curve itself, indicating the absence of entrapped water in the gel in these regions. The results afford direct experimental evidence of the reality of the cavity theory of sorption-desorption hysteresis.

A Comparative Study of Aromaticity in Substituted Tetracyclic and Hexacyclic Thiophenes

We have studied the nature of aromaticity in expanded porphyrinic analogues of thiophenes formed by four and six thiophenes. Using density functional theory (DFT) we have analyzed the aromaticity of both the macrocycle and individual molecular fragments. We find paramagnetic annulenic ring currents in the case of tetracyclic molecules and diamagnetic annulenic ring currents for hexacyclic molecules. We have also studied the effect of substitution of benzene rings within the macrocycle. We find that as the number of benzene rings is increased the aromaticity increases for tetracyclic systems and decreases for hexacyclic systems. All the results have been analyzed with various microscopic parameters, including geometry, excitation gap, and NMR criteria.