Um estudo sobre a influência de defeitos de diferente natureza nas propriedades eletrônicas de nanotubos usando o método das ondas cilindricas linearizadas aumentadas

Os nanotubos de carbono e nitreto de boro são nano estruturas unidimensionais que apresentam comportamento tanto metálico quanto semicondutor, dependendo da sua quiralidade, exceto para os nanotubos de nitreto de boro que apresentam sempre características semicondutoras, caso não estejam dopados. Devido suas características eletrônicas, os nanotubos apresentam grandes possibilidades de aplicação em dispositivos de nanoeletrônica, tais como nanodiodos, nanotransistores e como elementos de interconexão, dentre outros. Por esta razão, é importante compreender como fatores externos agem sobre as propriedades de tais materiais. Um desses fatores externos é a introdução de defeitos nos nanotubos. Tais defeitos são a ausência de um ou mais átomos de carbono, pertencente ao nanotubo de carbono e, de nitrogênio ou boro, para os nanotubos de nitreto de boro, ou ainda, a substituição de átomos de carbono, nitrogênio ou boro por diferentes átomos na estrutura dos correspondentes nanotubos. Este trabalho apresenta um estudo teórico dos efeitos da introdução de defeitos, por substituição, nas propriedades eletrônicas dos nanotubos de carbono e nitreto de boro, via simulação ab-initio. Avaliam-se as estruturas de banda de energia e densidade de estados de nanotubos de carbono semicondutores e metálicos tipos armchair e zig-zag e apenas do tipo armchair para os nanotubos de nitreto de boro usando o método LACW – método das ondas cilíndricas linearizadas aumentadas. Além disso, devido a crescente importância dos nanotubos de nitreto de boro, fazemos um estudo sistematizado da estrutura eletrônica desses nanotubos, para uma supercélula formada por três células unitárias, usando dopagem intrínseca, bem como uma análise quantitativa, baseada na energia total e banda proibida, de estabilidade dessas estruturas.

Estudo das lignanas de Peperomia blanda (Piperaceae): abordagem de aspectos estruturais, metabólitos e biossintéticos

Pós-graduação em Química - IQ

Insight into the Effects of Fe Addition on the Local Structure and Electronic Properties of SrTiO3

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Inorganic Graphenylene: A Porous Two-Dimensional Material With Tunable Band Gap

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Experimental and theoretical studies of photoluminescence in Zns obtained by microwave-assisted solvothermal method

A shift of the photoluminescence (PL) emission was observed in ZnS prepared by microwave assisted solvothermal method with the increase of the time in microwave. In this work we reported a study of the optical behavior linking with the structural disorder according to XRD and FEG-TEM results. The reduction of intrinsic defects in the lattice is responsible for the decrease of electronic levels in the band gap changing the PL profile. This effect was confirmed by electronic structure calculations.

Determinação da estrutura de diferentes alcoóis terpênicos: um estudo teórico e experimental

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Study of the oxygen vacancy influence on magnetic properties of Fe- and Co-doped SnO2 diluted alloys

Transition-metal (TM)-doped diluted magnetic oxides (DMOs) have attracted attention from both experimental and theoretical points of view due to their potential use in spintronics towards new nanostructured devices and new technologies. In the present work, we study the magnetic properties of Sn0.96TM0.04O2 and Sn0.96TM0.04O1.98(V (O))(0.02), where TM = Fe and Co, focusing in particular in the role played by the presence of O vacancies nearby the TM. The calculated total energy as a function of the total magnetic moment per cell shows a magnetic metastability, corresponding to a ground state, respectively, with 2 and 1 mu(B)/cell, for Fe and Co. Two metastable states, with 0 and 4 mu(B)/cell were found for Fe, and a single value, 3 mu(B)/cell, for Co. The spin-crossover energies (E (S)) were calculated. The values are E (S) (0/2) = 107 meV and E (S) (4/2) = 25 meV for Fe. For Co, E (S) (3/1) = 36 meV. By creating O vacancies close to the TM site, we show that the metastablity and E (S) change. For iron, a new state appears, and the state with zero magnetic moment disappears. The ground state is 4 mu(B)/cell instead of 2 mu(B)/cell, and the energy E (S) (2/4) is 30 meV. For cobalt, the ground state is then found with 3 mu(B)/cell and the metastable state with 1 mu(B)/cell. The spin-crossover energy E (S) (1/3) is 21 meV. Our results suggest that these materials may be used in devices for spintronic applications that require different magnetization states.

Hydrogen bond and the resonance effect on the formamide-water complexes

The interaction of formamide and the two transition states of its amide group rotation with one, two, or three water molecules was studied in vacuum. Great differences between the electronic structure of formamide in its most stable form and the electronic structure of the transition states were noticed. Intermolecular interactions were intense, especially in the cases where the solvent interacted with the amide and the carbonyl groups simultaneously. In the transition states, the interaction between the lone pair of nitrogen and the water molecule becomes important. With the aid of the natural bond orbitals, natural resonance theory, and electron localization function (ELF) analyses an increase in the resonance of planar formamide with the addition of successive water molecules was observed. Such observation suggests that the hydrogen bonds in the formamidewater complexes may have some covalent character. These results are also supported by the quantitative ELF analyses. (C) 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012

Site localization of Cd impurities in sapphire

By combining first-principles electronic structure calculations and existing time-differential gamma-gamma perturbed-angular-correlation experiments we studied the site localization, the local environment, and the electronic structure of Cd impurities in sapphire (alpha-Al2O3) single crystals in different charged states. The ab initio calculations were performed with the full-potential augmented plane wave plus local orbitals method and the projector augmented wave method. Comparing the calculated electric-field-gradient tensor at the Cd nuclei in the alpha-Al2O3 host lattice and the corresponding available experimental values, we have seen that it is equally possible for Cd to replace an Al atom (in a negative charge state) or to be placed in an interstitial site (in a neutral charge state). To finally address the issue of the Cd impurity localization, we performed formation energy calculations. These results have shown that Cd placed in the substitutional Al site, in the negatively charged state, is the most probable configuration.

CdSe/CdTe interface band gaps and band offsets calculated using spin-orbit and self-energy corrections

We performed ab initio calculations of the electronic structures of bulk CdSe and CdTe, and their interface band alignments on the CdSe in-plane lattice parameters. For this, we employed the LDA-1/2 self-energy correction scheme [L.G. Ferreira, M. Marques, L.K. Teles, Phys. Rev. B 78 (2008) 125116] to obtain corrected band gaps and band offsets. Our calculations include the spin-orbit effects for the bulk cases, which have shown to be of importance for the equilibrium systems and are possibly degraded in these strained semiconductors. Therefore, the SO showed reduced importance for the band alignment of this particular system. Moreover, the electronic structure calculated along the transition region across the CdSe/CdTe interface shows an interesting non-monotonic variation of the band gap in the range 0.8-1.8 eV, which may enhance the absorption of light for corresponding frequencies at the interface between these two materials in photovoltaic applications. (C) 2012 Elsevier B.V. All rights reserved.

Structure and electronic properties of hydrated mesityl oxide: a sequential quantum mechanics/molecular mechanics approach

The hydration of mesityl oxide (MOx) was investigated through a sequential quantum mechanics/molecular mechanics approach. Emphasis was placed on the analysis of the role played by water in the MOx syn-anti equilibrium and the electronic absorption spectrum. Results for the structure of the MOx-water solution, free energy of solvation and polarization effects are also reported. Our main conclusion was that in gas-phase and in low-polarity solvents, the MOx exists dominantly in syn-form and in aqueous solution in anti-form. This conclusion was supported by Gibbs free energy calculations in gas phase and in-water by quantum mechanical calculations with polarizable continuum model and thermodynamic perturbation theory in Monte Carlo simulations using a polarized MOx model. The consideration of the in-water polarization of the MOx is very important to correctly describe the solute-solvent electrostatic interaction. Our best estimate for the shift of the pi-pi* transition energy of MOx, when it changes from gas-phase to water solvent, shows a red-shift of -2,520 +/- 90 cm(-1), which is only 110 cm(-1) (0.014 eV) below the experimental extrapolation of -2,410 +/- 90 cm(-1). This red-shift of around -2,500 cm(-1) can be divided in two distinct and opposite contributions. One contribution is related to the syn -> anti conformational change leading to a blue-shift of similar to 1,700 cm(-1). Other contribution is the solvent effect on the electronic structure of the MOx leading to a red-shift of around -4,200 cm(-1). Additionally, this red-shift caused by the solvent effect on the electronic structure can by composed by approximately 60 % due to the electrostatic bulk effect, 10 % due to the explicit inclusion of the hydrogen-bonded water molecules and 30 % due to the explicit inclusion of the nearest water molecules.

Very Intense Distinct Blue and Red Photoluminescence Emission in MgTiO3 Thin Films Prepared by the Polymeric Precursor Method: An Experimental and Theoretical Approach

MgTiO3 (MTO) thin films were prepared by the polymeric precursor method with posterior spin-coating deposition. The films were deposited on Pt(111)/Ti/SiO2/Si(100) substrates and heat treated at 350 degrees C for 2 h and then heat treated at 400, 450, 500, 550, 600, 650 and 700 C for 2 h. The degree of structural order disorder, optical properties, and morphology of the MTO thin films were investigated by X-ray diffraction (XRD), micro-Raman spectroscopy (MR), ultraviolet-visible (UV-vis) absorption spectroscopy, photoluminescence (PL) measurements, and field-emission gun scanning electron microscopy (FEG-SEM) to investigate the morphology. XRD revealed that an increase in the annealing temperature resulted in a structural organization of MTO thin films. First-principles quantum mechanical calculations based on density functional theory (B3LYP level) were employed to study the electronic structure of ordered and disordered asymmetric models. The electronic properties were analyzed, and the relevance of the present theoretical and experimental results was discussed in the light of PL behavior. The presence of localized electronic levels and a charge gradient in the band gap due to a break in the symmetry are responsible for the PL in disordered MTO lattice.

Rare-earth impurities in gallium nitride: The role of the Hubbard potential

We performed a first principles investigation on the electronic properties of 4f-rare earth substitutional impurities in zincblende gallium nitride (GaN:REGa, with RE=Eu, Gd, Tb, Dy, Ho, Er and Tm). The calculations were performed within the all electron methodology and the density functional theory. We investigated how the introduction of the on-site Hubbard U potential (GGA + U) corrects the electronic properties of those impurities. We showed that a self-consistent procedure to compute the Hubbard potential provides a reliable description on the position of the 4f-related energy levels with respect of the GaN valence band top. The results were compared to available data coming from a recent phenomenological model. (C) 2012 Elsevier B.V. All rights reserved.

Structure and dynamics of supramolecular assemblies studied by advanced solid-state NMR spectroscopy

Ziel der vorliegenden Arbeit ist die Aufklärung von Struktur und Dynamik komplexer supramolekularer Systeme mittels Festkörper NMR Spektroskopie. Die Untersuchung von pi-pi Wechselwirkungen, welche einen entscheidenden Einfluss auf die strukturellen und dynamischen Eigenschaften supra- molekularer Systeme haben, hilft dabei, die Selbst- organisationsprozesse dieser komplexen Materialien besser zu verstehen. Mit dipolaren 1H-1H and 1H-13C Wiedereinkopplungs NMR Methoden unter schnellem MAS können sowohl 1H chemische Verschiebungen als auch dipolare 1H-1H und 1H-13C Kopplungen untersucht werden, ohne dass eine Isotopenmarkierung erforderlich ist. So erhält man detaillierte Informationen über die Struktur und die Beweglichkeit einzelner Molekül- segmente. In Verbindung mit sogenannten nucleus independent chemical shift (NICS) maps (berechnet mit ab-initio Methoden) lassen sich Abstände von Protonen relativ zu pi-Elektronensystemen bestimmen und so Strukturvorschläge ableiten. Mit Hilfe von homo- und heteronuklearen dipolaren Rotationsseitenbandenmustern könnenaußerdem Ordnungs- parameter für verschiedene Molekülsegmente bestimmt werden. Die auf diese Weise gewonnenen Informationen über die strukturellen und dynamischen Eigenschaften supramolekularer Systeme tragen dazu bei, strukturbestimmende Molekül- einheiten und Hauptordnungsphänomene zu identifizieren sowie lokale Wechselwirkungen zu quantifizieren, um so den Vorgang der Selbstorganisation besser zu verstehen.

Quantum effects and dynamics in hydrogen-bonded systems: a first-principles approach to spectroscopic experiments

Computer simulations have become an important tool in physics. Especially systems in the solid state have been investigated extensively with the help of modern computational methods. This thesis focuses on the simulation of hydrogen-bonded systems, using quantum chemical methods combined with molecular dynamics (MD) simulations. MD simulations are carried out for investigating the energetics and structure of a system under conditions that include physical parameters such as temperature and pressure. Ab initio quantum chemical methods have proven to be capable of predicting spectroscopic quantities. The combination of these two features still represents a methodological challenge. Furthermore, conventional MD simulations consider the nuclei as classical particles. Not only motional effects, but also the quantum nature of the nuclei are expected to influence the properties of a molecular system. This work aims at a more realistic description of properties that are accessible via NMR experiments. With the help of the path integral formalism the quantum nature of the nuclei has been incorporated and its influence on the NMR parameters explored. The effect on both the NMR chemical shift and the Nuclear Quadrupole Coupling Constants (NQCC) is presented for intra- and intermolecular hydrogen bonds. The second part of this thesis presents the computation of electric field gradients within the Gaussian and Augmented Plane Waves (GAPW) framework, that allows for all-electron calculations in periodic systems. This recent development improves the accuracy of many calculations compared to the pseudopotential approximation, which treats the core electrons as part of an effective potential. In combination with MD simulations of water, the NMR longitudinal relaxation times for 17O and 2H have been obtained. The results show a considerable agreement with the experiment. Finally, an implementation of the calculation of the stress tensor into the quantum chemical program suite CP2K is presented. This enables MD simulations under constant pressure conditions, which is demonstrated with a series of liquid water simulations, that sheds light on the influence of the exchange-correlation functional used on the density of the simulated liquid.