Dissertações em Física (Mestrado) - PPGF/ICEN

URI Permanente para esta coleçãohttps://repositorio.ufpa.br/handle/2011/2340

O Mestrado Acadêmico iniciou-se em 2003 e pertence ao Programa de Pós-Graduação em Física (PPGF) do Instituto de Ciências Exatas e Naturais (ICEN) da Universidade Federal do Pará (UFPA).

Navegar

Agora exibindo 1 - 20 de 39

Acesso aberto (Open Access)
Análise da potencialidade a condução do BDT através da densidade eletrônica de estados via tight binding e desenvolvimento de software (B3J)
(Universidade Federal do Pará, 2007) GUIMARÃES, Jeconias Rocha; DEL NERO, Jordan; http://lattes.cnpq.br/5168545718455899
In this work we studied the potentiality of the polymer BDT (1,3-benzodithiole 4Hciclopenta[2,1-b:3,4b’]) to become a conducting polymer. Ground state conformations and the electronic structure have been calculated through quantum chemical methods in order to obtain the density of electronic states. The presence of several types of conformational defects and the variation of doping level has been considered. One of the most used theories to study the doping effects on conjugated polymers is the Huckel method. It is based on the separability of the sigma and pi bonds of planar molecules. BDT oligomers are not planar molecules and an extended Huckel method that includes all the atomic valence functions has been used. An original computation code, the B3J program, has been developed for this purpose. Simulations of the absorption spectrum in the UV-visible-near IR region have seen performed as well. Program B3J calculates the density of states of polymeric systems. The band structure of BDT was obtained with this software. We calculated the density of states of the neutral system and doped systems including several doping levels and both random and uniform distribution of defects. The square of the coefficients expansion of the wave function was obtained for polymers including up to 20 monomers. For these calculations we used geometries calculated by AM1 and PM3 quantum chemical methods. Finally, we studied the asymmetry of the charge separation induced by the presence of an external static electrical field in BDT oligomers suitably substituted by electron acceptor/donor species. The results are consistent with a transistor-like behavior of neutral and charged molecules.
Acesso aberto (Open Access)
Caracterização de polímeros unidimensionais (Poliacetileno, Poliazina e Poliazoeteno) através de cálculos espectroscópicos e transporte eletrônico
(Universidade Federal do Pará, 2010) LEAL, José Fernando Pereira; DEL NERO, Jordan; http://lattes.cnpq.br/5168545718455899
In this work is presented a theoretical investigation of the neutral and bipolarononlike ground and excited states of molecules and polymers isoelectronic composed by Polyacetylene, Polyazine and Polyazoethene. The results obtained, utilizing DFT and ab initio methodologies, reveal that a very good defects description can be important in the investigation of insulator-metal transition of quasi-unidimensional polymers indicating metallic behavior around the Fermi level as mechanism of conductivity of polymers. This result is consistent with experimental data and do not anticipate by Su-Schrieffer-Heeger (SSH) methodology. These results are consistent with significant features as a nanodevice and can be summarized as: (i) it could be used as single directional molecular rectiffer with a conformational geometry with small lead coupling; (ii) our non-equilibrium green function simulation present that Polyacetylene, Polyazine and Polyazoethene could rectifield without gate current; (iii) based on properties of bonds type, it can be utilized to design devices with applications in molecular electronics.
Acesso aberto (Open Access)
Crescimento e caracterização dos cristais de sulfato de níquel hexahidratado dopados com íons [MnH2O]2+ e com sulfato de magnésio heptahidratado
(Universidade Federal do Pará, 2011) FERREIRA JÚNIOR, Messias de Nazaré Guimarães; REMÉDIOS, Cláudio Márcio Rocha; http://lattes.cnpq.br/7146076994037490
In this work, manganese ions doped nickel sulphate crystals (NSH:Mn) and magnesium ion doped nickel sulphate crystals (NMgSH) were grown and later characterized by X-ray diffraction and Raman spectroscopy techniques. The results obtained showed that the doped crystals possess a structure very similar to that of the pure nickel sulphate crystal (NSH), with an anisotropic deformation in the unit cell dimensions compared to the pure crystal, undergoing expansion in unit. The aim of the present study was to grow two new single crystals of good optical quality to be used as optical bandpass filters. Nickel sulfate hexahydrate (NHS) crystals are known to possess an optical transmission spectrum which has attracted much attention because it presents two regions with high transmission efficiency of approximately 80%, the first region being between 200 and 350 nm and the second between 400 and 600 nm, and a high absorption efficiency in other regions of the UV-VIS spectrum. A light transmission spectrum with these characteristics is similar to an optical filter. Termogravimetric (TGA) analyses were carried out for pure and doped crystals. The obtained decomposition temperature of NSH was found to be 73 °C while that NSH: Mn and NMgSH crystals present values of 82 ° C and 86 C respectively. As can be easily perceived, the thermal stability of crystals with Mn or Mg ions in their structures is significantly higher. The transmission band between 200 and 350 nm in the optical spectrum of NSH was found to be narrower in the transmission spectrum of the doped crystal thus restricting the region of the spectrum known as UVA.
Acesso aberto (Open Access)
Criação de fótons no efeito Casimir dinâmico em cavidade oscilante com condições de Neumann e Dirichlet
(Universidade Federal do Pará, 2005-03) GRANHEN, Edney Ramos; ALVES, Danilo Teixeira; http://lattes.cnpq.br/6642002445572793
We consider a massless scalar field in a two-dimensional space-time inside an oscillating cavity with mixed boundary conditions. In order to discuss particle creation phenomenum, we consider the situation of parametric resonance in which the oscillating frequency is twice the frequency of the first mode of the static cavity. For convenience, we suppose that one of the boundaries is at rest and imposes Neumann condition to the field, whereas the other is in non-relativistic motion and imposes a Dirichlet condition on the field. Following the procedure developed by Dodonov and Klimov (Phys. Rev. A, 56, 2664 (1996)), we compute the number of created particles, the generation rate and the energy in the cavity. We compare our results with those found in the literature for the Dirichlet-Dirichlet case.
Acesso aberto (Open Access)
Densidade de energia e força de radiação sobre fronteiras em movimento num espaço-tempo bidimensional
(Universidade Federal do Pará, 2009-03) REGO, Andreson Luis Carvalho; ALVES, Danilo Teixeira; http://lattes.cnpq.br/6642002445572793
In the present work, we investigate the energy density and the quantum radiation reaction force on one moving boundary which imposes on a massless scalar field a Dirichlet or a Neumann boundary condition. Though we assume a particular motion for the boundary, introduced by Walker and Davies many years ago (J. Phys. A, 15 L477, 1982), we consider new possibilities for the initial field state, namely, thermal state and coherent state. We also investigate the problem of a cavity with one of the boundaries in the particular motion proposed by Walker and Davies, taking into account the vacuum, thermal and coherent initial field states. Finnaly we investigate the case of a non-static boundary which imposes the Robin boundary condition to the field.
Acesso aberto (Open Access)
Densidade de energia e força de radiação sobre fronteiras em movimento para estados arbitrários do campo: aplicação ao estado coerente
(Universidade Federal do Pará, 2008-08-29) LIMA, Mateus Gomes; ALVES, Danilo Teixeira; http://lattes.cnpq.br/6642002445572793
In this work we consider a real massless scalar field in a two-dimensional spacetime, satisfying Dirichlet or Neumann boundary condition at the instantaneous position of a moving boundary. For a relativistic law of motion, we show that Dirichlet and Neumann boundary conditions yield the same radiation force on a moving mirror when the initial field state is invariant under time translations. We obtain the exact formulas for the energy density of the field and the radiation force on the boundary for vacuum, coherent and squeezed state. In the nonrelativistic limit, our results coincide with those found in the literature. We also investigate the field inside an oscillating cavity. Considering Neumann and Dirichlet boundary conditions, we write the exact formula for the energy density inside a non-static cavity for an arbitrary initial field state. Taking as basis the Moore equation, we calculate recursively the energy density and investigate its time evolution for the coherent state.
Acesso aberto (Open Access)
Difração de policristais e difração múltipla de raios X para o estudo da influência dos íons Mn+2, Mg+2 e Cu+2 nas estruturas cristalinas da L asparagina monohidratada e do sulfato de níquel hexahidratado
(Universidade Federal do Pará, 2012) MELO, Geraldo Souza de; REMÉDIOS, Cláudio Márcio Rocha; http://lattes.cnpq.br/7146076994037490
In this work we accomplished a study about the influence of doping Mn+2, Mg+2 and Cu+2 in the crystal structures of crystals of nickel sulfate hexahydrate (NSH) and L Asparagine Monohydrate (LAM). The introduction of dopants in a crystal lattice must change its physical properties or growth habit. These changes must promote the technological applications of these crystals in many areas like medicine, agriculture, optics and electronics. The NSH crystals were grown by the slow evaporation method of the solvent and doped with ions of Mn+2 and Mg+2, resulting in crystals of good quality. We measures method of X-ray diffraction of the pure crystals and polycrystalline doped and from the results obtained we refinements, using the method of Rietiveld where was observed that the same crystal structure doped showed the same tetragonal and space group that the pure crystal, having a little change in their lattice parameters and volume of its unit cells. We observed that the introduction of dopants caused changes in the lengths of the links and the angles between the nickel and oxygen atoms, this may explain why the temperature of dehydration crystals NSH:Mn and NSH:Mg is bigger than that of pure NSH. We use the X-ray Diffraction Multiple technique with synchrotron radiation in differents energies on the workstation XRD1, of the National Synchrotron Light Laboratory (LNLS) in order to identify possible changes in the structures of doped crystals of nickel sulphate and L Asparagine. The Renninger diagrams show changes in the intensity, profile and position of the secondary peaks of doped crystals caused by the introduction of dopants. The crystals were grown L Asparagine monohydrate by the method of slow solvent evaporation, and doped with ions of Cu+2. The diffraction measurements showed that the doped crystal has the same orthorhombic structure that the pure crystal. Our results indicate that the incorporation mechanisms of the Cu+2 ions in the crystal lattice of Asparagine Monohydrate L occur in interstitial form. Changes were detected in intensity as well as in the positions and profile diagrams Renninger secondary peaks in the crystal doped.
Acesso aberto (Open Access)
Difração de raios X em minerais de bauxita e análise através de refinamento pelo método de Rietveld
(Universidade Federal do Pará, 2011) ERDÓCIA, Félix Anderson Barros; REMÉDIOS, Cláudio Márcio Rocha; http://lattes.cnpq.br/7146076994037490
The aluminum metal is obtained from bauxite ore, great industrial importance, consisting of one or more types of aluminum hydroxide plus a mixture of compounds containing silica, iron oxide, titania and aluminosilicates. Because of the variation in the relative concentration of these components in different samples of bauxite, the qualitative and quantitative mineralogy of the ore, has great importance with regard to its technological application, since this is directly related to the content of these components. This work was applied in eight samples of bauxite, extracted from a mine in Paragominas, the process of refining the spectra of X-ray diffraction using the Rietveld method, which were identified and quantified the crystalline phases: gibbsite, kaolinite, goehtita, anatase, quartz and hematite. Carried the refinements of the samples, we found that all had high levels of Gibbsite and Goethite low which gives an excellent type of bauxite to be used in extraction of alumina.
Acesso aberto (Open Access)
Efeito Casimir em teorias de Chern-Simons
(Universidade Federal do Pará, 2011) RODRIGUES, Penn Lee Menezes; PEREZ, Silvana; http://lattes.cnpq.br/3585326481456738
In this work we study the Casimir force for Maxwell-Chern-Simons (MCS) theories in (2+1) dimensions. In particular for the bidimensional case, we consider di erent boundary conditions and present new results concerning the in uence of the temperature in the phenomenon. We also analyse the Temperature Inversion Symmetry, considering both the massless and massive cases. We start by studying general aspects from Matsubara formalism with the goal of introduce thermal e ects in the theory; we also analyse general aspects of (2+1)-dimensional MCS theory. Then, we review the Casimir force for the in nite magnetically permeable lines at both zero and nite temperature, as well as the mixed lines at zero temperature, for which we take one line in nite magnetically permeable and the other perfect conducting. We next present new results concerning the Thermal Casimir force for the case of mixed lines. Finally, we analyse the Temperature Inversion Symmetry associated with the Helmholtz free energy, showing that even for the mixed lines boundary conditions it is still possible to de ne a residual symmetry, the result being analogous to previous results for the eletrodynamics in (3+1) dimensions.
Acesso aberto (Open Access)
Efeitos de temperatura e potencial químico em Teoria Quântica de Campos
(Universidade Federal do Pará, 2009-03) MACIEL, Soraya Galdino; PEREZ, Silvana; http://lattes.cnpq.br/3585326481456738
In this work we study the e ects of a nonzero chemical potential in (1 + 1) dimensions quantum eld models at nite temperature. We particularly consider massless fermions in an abelian gauge eld background and calculate the e ective action by evaluating the n-point functions. We nd that the structure of the amplitudes corresponds to a generalization of the structure noted earlier in a calculation found in the literature without a chemical potential (the associated integrals carry the dependence on the chemical potential). Our calculation shows that the chiral anomaly is una ected by the presence of a chemical potential at nite temperature. However, unlike in the absence of a chemical potential, odd point functions do not vanish. In fact, we nd that all the even point functions are even functions of while the odd point functions are odd functions of . We show that the origin of the structure of the amplitudes is best seen from a formulation of the theory in terms of left and right handed spinors. The calculations are also much simpler in this formulation and it clari es many other aspects of the theory.
Acesso aberto (Open Access)
Espectrometria Raman, UV, DOS e Circular Dicroísmo de alcalóides do cigarro
(Universidade Federal do Pará, 2011-02-28) GUEDES, Alberto Monteiro; CHAVES NETO, Antonio Maia de Jesus; http://lattes.cnpq.br/3507474637884699
This work is about spectroscopic analysis of some molecular structures present in tobacco (Nicotiana glauca), the base for cigarette, and their interactions with the DNA molecule. According to its importance, among the variety present in the cigarette, the molecules studied were derived from nicotinic acid, nicotinic acid (niacin / vitamin B3), nicotinamide, trigonelline, nicotine, nornicotine and anabasine. The optimizations of these structures were initially obtained in the Hyperchem 7.5 computational software based on the theory of molecular mechanics. Then, they were optimized using the method Density Functional Theory, on the basis B3LYP/ 6-311 + + G (d, p), simulated in software Gaussian 03. Once the optimized structures, we obtained the UV absorption, Raman, Infrared, Circular Dichroism and Density of States spectra using Time-Dependent Density Functional Theory also simulated the in the same software. At the end of this process was also simulated, via molecular mechanics, the interactions of these structures with the DNA molecule in order to verify the potential carcinogenic or not these substances.
Acesso aberto (Open Access)
Espectroscopia de Lente Térmica aplicada ao sistema Ácido oléico/Beta Caroteno
(Universidade Federal do Pará, 2007) PASSOS, João Paulo Rocha dos; MOREIRA, Sanclayton Geraldo Carneiro; http://lattes.cnpq.br/7312223977002681
In this work we present a study in the mixture formed by the beta-carotene diluted in oleic acid in different concentrations being used for that the technique called of Thermal Lens. We tried to vary the different control parameters as: the thickness of the sample, his/her concentration, the potency of the excitation laser, etc. We applied the aberrant model developed by Shen to find the thermal diffusivity, the variation of the refraction index with the temperature (dn/dT), and the magnitude of the sign of thermal lens, in the samples. We verified, with base in the theoretical model presented in the chapter 2, that if the increase of the potency and of the concentration it is very big and it reaches a certain value, parameters as thermal diffusivity start to present distortions in the measured values. We also observed that the mixture BC:AO presents nonlinear absorption, even for small potencies of the excitation laser used. The contributions presented in this work are unpublished and they should contribute to a better understanding of the thermal properties of the system BC:AO or of similar systems as some vegetable oils that are rich in acid oleic and betacarotene.
Acesso aberto (Open Access)
Estudo de nanofios de Au e dendrímeros
(Universidade Federal do Pará, 2010-01-12) COSTA, José Francisco da Silva; CHAVES NETO, Antonio Maia de Jesus; http://lattes.cnpq.br/3507474637884699
First part of this work is about the classical molecular dynamics simulation of the interaction of matrix systems of parallel nanowires of Au as a function of time. The results find the time of collision between the wires of the array. The second part of this work is using classical molecular dynamics simulation for five generations of PAMAM dendrimers, each interacting individually with a carbon nanotube as a function of time resulting in a molecular motor. Furthermore, it were calculated the absorption spectra of this system and it was found that they could be nanomotors controlled by light. For all these systems were calculated kinetic energy, potential, speed, thermodynamic properties as molar entropy variation, molar heat capacity and temperature in situ. These quantities provide us with valuable information about the behavior of these systems.
Acesso aberto (Open Access)
Estudo de propriedades estruturais e de piezeletricidade nos cristais de ADP e KDP puros e dopados com íons Ni2+ e Mn3+ com DMRX utilizando radiação síncrotron
(Universidade Federal do Pará, 2010-08-31) GOMES, Eduardo José de Lima; REMÉDIOS, Cláudio Márcio Rocha; http://lattes.cnpq.br/7146076994037490
The X-ray multiple diffraction using synchrotron radiation has been applied to study transition metal cátions Mn 3+ and Ni 2+ incorporated into Ammonium Diydrogen Phosphate (ADP) Crystal lattice and potassium dihydrogen phosphate (KDP). The results shows that regarding peak positions and number of peaks all the profilets look almost identical. This fact alone tells us that the unit cell parameters and the crystal symmetry are practically the same regardless of the incorporation of Mn 3+ and Ni 2+ cations. Accurate calculation of the unit-cell parameters revels that the lattices lattices parameters a = b increase and lattices parameters c decrease following Ni 2+ and Mn 3+ incorporation. In the measurements for the two wavelengths ADP:Mn crystal exhibit asymmetric peak profiles and no extra peak appears in the whole Mn 3+ doped RS. On the other hand, in the ADP:Ni measurements one can clearly observe: (i) suppression of the intensity profile asymmetry in secondary peaks for the Ni 2+ doped RS (below l Ni 2+ Kedge) and also, (ii) marked asymmetry inversion (above l Ni 2+ Kedge), for example the peak (5-12) / (-112) which represents a four beam case. These results indicate that synchrotron radiation RS is a high resolution probe to be used in the impurity incorporation in the ADP lattice. Moreover we have investigated ADP:Mn, KDP:Mn and KDP:Ni crystals using X-ray diffraction at room temperature. The results of the measurements of 440 and 066 reflections allow obtaining the d 36 and d 25 coefficients. We reported on the experimental verification based on X-ray measurements, the d 36 piezoelectric coefficients increased with doping of the Mn and Ni 2+ in the KDP and in ADP crystals.
Acesso aberto (Open Access)
Estudo de solvatocromismo em líquidos moleculares orgânicos via método seqüencial Monte Carlo/Mecânica Quântica
(Universidade Federal do Pará, 2007-03) MARTINS, Hardiney dos Santos; DEL NERO, Jordan; http://lattes.cnpq.br/5168545718455899
The Sequential Monte Carlo / Quantum Mechanical method was applied to study the solvatochromic shifts and the dipole moments for organic molecules: Uracil in water, - carotene in oleic acid, ricinoleic acid in methanol and in ethanol and oleic acid in methanol and in ethanol. The optimizations and charges distributions had found by Density Functional Theory through the B3LYP functional and sets basis functions 6-31G(d) to all molecules except water and Uracil, whose was applied the sets basis functions 6-311++G(d,p). In the classical approach, Monte Carlo, was applied the algorithm Metropólis through the DICE program. The sampling of statistically relevant configurations to averaged calculations of the properties was used with auto-correlation function performed to each system. The Radial Distribution Function of the molecular liquids was applied to separate the first shell solvation for each system, which gives the main interaction between solute-solvent. The statistically relevant configurations of the first shell of solvation of the each system were subject a quantum mechanical calculations at the semi-empiric level with the method ZINDO/S-CI. The absorptions spectrum had found to solutes in gas phase and to the systems of molecular liquids spoken. The electric dipole moments of these were also found. All the bands of spectrum absorptions had a blue shift, except the second band of the -carotene in oleic acid that was a red shift. The results found have a very good agreement with the values found in the literature. All the system had increase in the electric dipole moments because the solvents molecules are polar molecules. The system of fatty acids in alcohols had results very similar, in other words, the fatty acids mentioned had characteristics spectroscopic similar submitted to same solvents. The simulations whose with Sequential Monte Carlo / Quantum Mechanical method were studied show the methodology is effective to find the spectroscopic proprieties of molecular liquids analyzed.
Acesso aberto (Open Access)
Fenômeno de interferência na densidade de energia em cavidades com duas fronteiras oscilantes
(Universidade Federal do Pará, 2009) PIRES, Wagner Pinheiro; ALVES, Danilo Teixeira; http://lattes.cnpq.br/6642002445572793
We consider a real massless scalar field inside a cavity with two moving mirrors in a two-dimensional spacetime, satisfying Dirichlet boundary condition at the instantaneous position of the boundaries, for arbitrary and relativistic laws of motion. Considering vacuum as the initial field state, we show that the exact value of the the energy density in the cavity can be obtained by tracing back a sequence of null lines, connecting the value of the energy density at the given spacetime point to a certain known value of the energy density at a point in the region where the initial field modes are not affected by the boundaries motion. We obtain formulas for the energy density of the field and the quantum force acting on the boundaries. We also show that for a large class of movements, including resonant cases found in the literature, the exact method proposed here enable us to find analytical solutions written as series in the parameter that controls the amplitudes of the movements. Using these analytical solutions, we investigate the interference phenomena in the energy density and total energy stored in the cavity.
Acesso aberto (Open Access)
Fonte escalar acoplada ao campo de Klein-Gordon orbitando um objeto estelar
(Universidade Federal do Pará, 2006-02) MEIRA FILHO, Damião Pedro; CRISPINO, Luís Carlos Bassalo; http://lattes.cnpq.br/4033994493756291
In this work we determine, using Quantum Field Theory in tree level, the scalar radiation emitted by a source in uniform circular motion in Minkowski spacetime, assuming Newtonian gravitation, and in the curved spacetime of a chargeless black hole with null angular momentum, assuming General Relativity. We perform this calculation analitically for the case of Minkowski spacetime and numerically for Schwarzschild spacetime. In the black hole case we obtain the analytic form and the normalization of the modes in the asymptotic regions. We verify, for stable circular orbits acording to general relativity, that the emitted power in Schwarzschild spacetime is lower than the one obtained in Minkowski spacetime assuming Newtonian gravitation. We obtain that only a little amount of the emitted radiation is absorbed by black hole. We also verify that the difference between the emitted powers in Schwarzschild and Minkowski cases decreases if the mass of ¯eld is increased. In Schwarzschild spacetime, the amount of radiation absorbed by the black hole increases for higher values of the mass of the scalar field.
Acesso aberto (Open Access)
As funções do grupo de renormalização no modelo com auto-interação quártica fermiônica
(Universidade Federal do Pará, 2009) NASCIMENTO, Leonardo Oliveira do; ALVES, Van Sérgio da Silva; http://lattes.cnpq.br/5346258049047843
Four femion interactions models have been studied to clarify their conceptual aspects and possible applications in quantum field theory. In this work we present the structure of the renormalization group in the Nambu-Jona-Lasinio model up to 1-loop order. The model is not perturbatively renormalizable in the usual power counting sense, but it is treated as an effective theory, valid in a scale of energy where p <<^, being p the external moment of the loop and ^ a massive parameter that characterizes the coupling of the non-renormalizable vertex. We clarify the tensorial structure of the interaction vertices and calculate the functions of the renormalization group. The analysis of the fixed points of the theory is also presented using Zimmermann procedure for reducing the coupling constants. We find that the origin is an infrared-stable fixed point at low energies and has also a nontrivial ultraviolet stable fixed point, indicating that the theory could be perturbatively investigated if the momentum is low enough.
Acesso aberto (Open Access)
Investigação da dinâmica sequêncial Monte Carlo/Mecânica Quântica para sitemas moleculares orgânicos
(Universidade Federal do Pará, 2007-03) GESTER, Rodrigo do Monte; DEL NERO, Jordan; http://lattes.cnpq.br/5168545718455899
The main objective of this work is to investigate theoretically the electronic and optical properties of organic compounds on liquid enviroment. The understanding of interactions on liquid systems is very important for the description of phenomena in many parts of the Science, like Physics, Chemistry, Biology and Materials. Also as in the development of optical materials. The thermal fluctuations make that lots of configurations can be generated. This is the reason of the statistical behavior realized in liquid systems. Considering these difficulties, to describe liquid systems, the sequential Monte Carlo / quantum mechanics (S-MC/QM) treatment is used in this work. On this procedure, first the liquid structure is generated by MC simulation and later, only the most important part of the system is treated as quantum mechanics.Using the above procedure, the quantum properties of the Methyl Orange (MO) and O 2,3-dimethyl thiene[3,4-b]pirazine (DTP) were investigated. MO is a well known pH indicator and can be found under basic and acidic conditions. Its minimal energy geometries were obtained by Density Functional Theory by the B3LYP functional, being the system described by Pople basis with one polarization function (6-31G*). To obtain the average properties of the quantum observables of these systems quantum chemistry calculations were performed within semi-empirical INDO/S-CI approach. About the absorption spectra of the MO, the experimental data presented in scientific literature reports a broad band placed on the lowest energies, more precisely between 400 and 600 nm. Our theoretical results for the alcaline form show an intense π → π* transition at about 432.4±0.03 nm and under acidic conditions, considering the MO acidic form, this transition appears at about 507.4±0.12, 496.4±0.28 or 545.3±0.10 nm, showing good agreement with experimental results. The DTP is a particular system used in the production of low band gap polimers. Its electrical and optical properties were obtained by the novel Average Solvent Electrostatic Configuration (ASEC) methodology. The ASEC procedure include a solvent molecules point charges and permits obtaining quantum mechanical quantities performing only few quantum calculations. For DTP, using the Mφller- Plesset second order perturbation thoery (MP2) and the aug-cc-pVDZ, the electric dipole moment 1.16 D was reached performing only four quantum calculations on representative configurations, presenting an increase of 42% when compared to the isolated dipole. The polarizability also was apparised considering the same level of dipole calculation, the average value 132.7 a30 was observed. The lowest energy region of the absorption spectra was also investigated by ASEC procedure and using both, semi-empirical and DFT quantum approaches. This absorption region is the reason of contraditory conclusions about of the n → π* and π → π* transitions. Our results show these excitations are observed and they can overlap themselves. As example, our DFT results using the B3LYP functional show that these transitions are placed at about 360.63 and 351.15 nm, respectively, being in good agreement with experimental predictions.
Acesso aberto (Open Access)
Investigação da transição isolante-metal do CDM via algoritmos computacionais e estudo de nano-dispositivos orgânicos
(Universidade Federal do Pará, 2007) AMAZONAS, Járlesson Gama; DEL NERO, Jordan; http://lattes.cnpq.br/5168545718455899
We present in this work a theoretical study on conjugated organic polymers. These systems, in general semiconductors or insulators, when doped, show an increase in electrical conductivity. Under action of electric field, small oligomers can present a similar behavior to of usual devices, but with innumerable advantages as, for example, size extremely reduced (some nanometers). In the first chapter we will make a brief introduction on organic polymers conjugated showing some experimental results for 4-dicianometileno-4,4-ciclopenta polymer [2,1-b: 3,4b'] ditiofeno - CDM, that is the central object of study. Chapter 2 deals with the used quantum methods. We will cite the Hartre-Fock (HF) approximation and its semiempirical derivations. The Configuration Interaction (CI) method and the Density Functional Theory (DFT) also will be treated in this chapter. Chapter 3 is dedicated to describe the characteristics of some usual devices as diodes and transistors. We will still cite some extremely small electronic devices. Chapter 4 describes our results and quarrels about the possibility the of the transistion insulator-metal in CDM when doped. We got the characterization optics of oligomers of CDM with null charge and in the presence of defects of the type bipolaron. From the Hartree-Fock level we calculate the Structure of Bands and the Density of States (DOS) for the PCDM in the neutral and doped state. The calculation of the DOS and the Dispersion had been carried through computational programs developed here in the Group GFMA. We still present in this chapter the theoretical absorption spectra for oligomers of CDM with geometry fully optimized by DFT. In chapter 5 we have the relative results to the analysis of nanodevice based on tetramers of CDM with and without charge. The curves of the charge displacement versus voltage present characteristics of curves of usual devices. We also analyze the theoretical absorption spectra of the nanodevice for values of null tension and in points of current saturation.