Efficiency vs. Stability in a Mixed Network Formation Model

Documentos de Trabajo

I. Site effects and exciton structure in molecular crystals - Benzene. II. The first and second triplet states of solid benzene

The effect of intermolecular coupling in molecular energy levels (electronic and vibrational) has been investigated in neat and isotopic mixed crystals of benzene. In the isotopic mixed crystals of C₆H₆, C₆H₅D, m-C₆H₄D₂, p-C₆H₄D₂, sym-C₆H₃D₃, C₆D₅H, and C₆D₆ in either a C₆H₆ or C₆D₆ host, the following phenomena have been observed and interpreted in terms of a refined Frenkel exciton theory: a) Site shifts; b) site group splittings of the degenerate ground state vibrations of C₆H₆, C₆D₆, and sym-C₆H₃D₃; c) the orientational effect for the isotopes without a trigonal axis in both the ¹B_2u electronic state and the ground state vibrations; d) intrasite Fermi resonance between molecular fundamentals due to the reduced symmetry of the crystal site; and e) intermolecular or intersite Fermi resonance between nearly degenerate states of the host and guest molecules. In the neat crystal experiments on the ground state vibrations it was possible to observe many of these phenomena in conjunction with and in addition to the exciton structure.

To theoretically interpret these diverse experimental data, the concepts of interchange symmetry, the ideal mixed crystal, and site wave functions have been developed and are presented in detail. In the interpretation of the exciton data the relative signs of the intermolecular coupling constants have been emphasized, and in the limit of the ideal mixed crystal a technique is discussed for locating the exciton band center or unobserved exciton components. A differentiation between static and dynamic interactions is made in the Frenkel limit which enables the concepts of site effects and exciton coupling to be sharpened. It is thus possible to treat the crystal induced effects in such a fashion as to make their similarities and differences quite apparent.

A calculation of the ground state vibrational phenomena (site shifts and splittings, orientational effects, and exciton structure) and of the crystal lattice modes has been carried out for these systems. This calculation serves as a test of the approximations of first order Frenkel theory and the atom-atom, pair wise interaction model for the intermolecular potentials. The general form of the potential employed was V(r) = Be^-Cr - A/r⁶ ; the force constants were obtained from the potential by assuming the atoms were undergoing simple harmonic motion.

In part II the location and identification of the benzene first and second triplet states (³B_1u and ³E_1u) is given.

Coincidence point theorems in quasi-metric spaces without assuming the mixed monotone property and consequences in G-metric spaces

In this paper, we present some coincidence point theorems in the setting of quasi-metric spaces that can be applied to operators which not necessarily have the mixed monotone property. As a consequence, we particularize our results to the field of metric spaces, partially ordered metric spaces and G-metric spaces, obtaining some very recent results. Finally, we show how to use our main theorems to obtain coupled, tripled, quadrupled and multidimensional coincidence point results.

Efficient electronic implementations of adaptive systems for ambient intelligence environments

183 p.

Electronic properties of graphene grain boundaries

Grain boundaries and defect lines in graphene are intensively studied for their novel electronic and magnetic properties. However, there is not a complete comprehension of the appearance of localized states along these defects. Graphene grain boundaries are herein seen as the outcome of matching two semi-infinite graphene sheets with different edges. We classify the energy spectra of grain boundaries into three different types, directly related to the combination of the four basic classes of spectra of graphene edges. From the specific geometry of the grains, we are able to obtain the band structure and the number of localized states close to the Fermi energy. This provides a new understanding of states localized at grain boundaries, showing that they are derived from the edge states of graphene. Such knowledge is crucial for the ultimate tailoring of electronic and optoelectronic applications.

Defect and structural imperfection effects on the electronic properties of BiTeI surfaces

The surface electronic structure of the narrow-gap seminconductor BiTeI exhibits a large Rashba-splitting which strongly depends on the surface termination. Here we report on a detailed investigation of the surface morphology and electronic properties of cleaved BiTeI single crystals by scanning tunneling microscopy, photoelectron spectroscopy (ARPES, XPS), electron diffraction (SPA-LEED) and density functional theory calculations. Our measurements confirm a previously reported coexistence of Te- and I-terminated surface areas

Effect of lithium-potassium mixed alkali on spectroscopic properties of Er3+-doped aluminophosphate glasses

Er3+-doped lithium-potassium mixed alkali aluminophosphate glasses belonging to the oxide system xK(2)O-(15x)Li2O-4B(2)O(3)-11Al(2)O(3)-5BaO-65P(2)O(5) are obtained in a semi-continuous melting quenching process. Spectroscopic properties of Er3+-doped glass matrix have been analysed by fitting the experimental data with the standard Judd-Ofelt theory. It is observed that Judd-Ofelt intensity parameters-Omega(t)(t=2, 4 and 6) of Er3+ change when the second alkali is introduced into glass matrix. The variation of line strength S-ed[I-4(13/2),I-4(15/2)] follows the same trend as that of the Omega(6) parameter. The effect of mixed alkali on the spectroscopic properties of the aluminophosphate glasses, such as absorption cross-section, stimulated emission cross-section, spontaneous emission probability, branching ratio and the radiative lifetime, has also been investigated in this paper.

Judd-Ofelt intensity parameters of Er3+ doped mixed alkali aluminophosphate glasses

Lithium sodium mixed alkali aluminophosphate glasses of the composition xNa(2)O-(15-x)Li2O-4B(2)O(3)-11Al(2)O(3)-5BaO-65P(2)O(5) (where x=0, 3.75, 7.5, 11.25 and 15 mol%) containing 0.5 mol% Er2O3 were prepared by melt quenching. The absorption spectra of Er3+ were studied from the experimental oscillator strengths and the Judd-Ofelt intensity parameters were obtained. The variations of Judd-Ofelt intensity parameters (Omega(2), Omega(4) and Omega(6)), experimental oscillator strengths of certain excited states of Er3+ and hypersensitive band positions with different mixed alkali content have been discussed in detail. It was found that there were similar effects of mixed alkali on both Judd-Ofelt intensity parameter 02 and the experimental oscillator strength of the hypersensitive transition, I-4(15/2) -> H-2(11/2). No shifts in the peak wavelength of the studied transitions were found in different glasses. (c) 2006 Elsevier B.V. All rights reserved.

Structural Integration of Tellurium Oxide into Mixed-Network-Former Glasses: Connectivity Distribution in the System NaPO3–TeO2

FSodium phosphate tellurite glasses in the system (NaPO3)(x)(TeO2)(1-x) were prepared and structurally characterized by thermal analysis, vibrational spectroscopy, X-ray photoelectron spectroscopy (XPS) and a variety of complementary solid-state nuclear magnetic resonance (NMR) techniques. Unlike the situation in other mixed-network-former glasses, the interaction between the two network formers tellurium oxide and phosphorus oxide produces no new structural units, and no sharing of the network modifier Na2O takes place. The glass structure can be regarded as a network of interlinked metaphosphate-type P(2) tetrahedral and TeO4/2 antiprismotic units. The combined interpretation of the O 1s XPS data and the P-31 solid-state NMR spectra presents clear quantitative evidence for a nonstatistical connectivity distribution. Rather the formation of homootomic P-O-P and Te-O-Te linkages is favored over mixed P-O-Te connectivities. As a consequence of this chemical segregation effect, the spatial sodium distribution is not random, as also indicated by a detailed analysis of P-31/No-23 rotational echo double-resonance (REDOR) experiments. ACHTUNGTRENUNG(TeO2)1 x were prepared and structurally characterized by thermal analysis,vibrat ional spectroscopy,X-ray photoelectron spectroscopy (XPS) and a variety of complementary solid-state nuclear magnetic resonance (NMR) techniques. Unlike the situation in other mixed-network-former glasses,the interaction between the two network formers tellurium oxide and phosphorus oxide produces no new structural units,and no sharing of the network modifier Na2O takes place. The glass structure can be regarded as a network of interlinked metaphosphate-type P(2) tetrahedral and TeO4/2 antiprismatic units. The combined interpretation of the O 1s XPS data and the 31P solid-state NMR spectra presents clear quantitative evidence for a nonstatistical connectivity distribution. Rather,the formation of homoatomic P O P and Te O Te linkages is favored over mixed P O Te connectivities. As a consequence of this chemical segregation effect,the spatial sodium distribution is not random,as also indicated by a detailed analysis of 31P/23Na rotational echo double-resonance (REDOR) experiments.

Effect of lithium-sodium mixed-alkali on phase transformation kinetics in Er3+/Yb3+ co-doped aluminophosphate glasses

Er3+ doped aluminophosphate glasses with various Na2O/Li2O ratios were prepared at 1250 degrees C using a silica crucible to study mixed alkali effect (MAE). The effect of relative alkali content on glass transition temperature, crystallization temperature and thermal stability were investigated using differential scanning calorimetry (DSC). In addition, apparent activation energies for crystallization, E, were determined employing the Kissinger equation. The effect of Al2O3 content on the magnitude of MAE was also discussed. No mixed-alkali effect is observed on crystallization temperature. (c) 2006 Elsevier B.V. All rights reserved.