Efeito túnel multidimensional em reações nucleares

Pós-graduação em Física - IFT

Coordenadas vestidas: formulação segundo a interpretação de Dirac-Feynman para a mecânica quântica e aplicações em CQED

Pós-graduação em Física - IFT

Accurate ab initio potential energy surfaces for the (3)A '' and (3)A ' electronic states of the O(P-3) plus HBr system

In this work, we report the construction of potential energy surfaces for the (3)A '' and (3)A' states of the system O(P-3) + HBr. These surfaces are based on extensive ab initio calculations employing the MRCI+Q/CBS+SO level of theory. The complete basis set energies were estimated from extrapolation of MRCI+Q/aug-cc-VnZ(-PP) (n = Q, 5) results and corrections due to spin-orbit effects obtained at the CASSCF/aug-cc-pVTZ(-PP) level of theory. These energies, calculated over a region of the configuration space relevant to the study of the reaction O(P-3) + HBr -> OH + Br, were used to generate functions based on the many-body expansion. The three-body potentials were interpolated using the reproducing kernel Hilbert space method. The resulting surface for the (3)A '' electronic state contains van der Waals minima on the entrance and exit channels and a transition state 6.55 kcal/mol higher than the reactants. This barrier height was then scaled to reproduce the value of 5.01 kcal/mol, which was estimated from coupled cluster benchmark calculations performed to include high-order and core-valence correlation, as well as scalar relativistic effects. The (3)A' surface was also scaled, based on the fact that in the collinear saddle point geometry these two electronic states are degenerate. The vibrationally adiabatic barrier heights are 3.44 kcal/mol for the (3)A '' and 4.16 kcal/mol for the (3)A' state. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4705428]

Coupled Boltzmann calculation of mixed axion/neutralino cold dark matter production in the early universe

We calculate the relic abundance of mixed axion/neutralino cold dark matter which arises in R-parity conserving supersymmetric (SUSY) models wherein the strong CP problem is solved by the Peccei-Quinn (PQ) mechanism with a concommitant axion/saxion/axino supermultiplet. By numerically solving the coupled Boltzmann equations, we include the combined effects of 1. thermal axino production with cascade decays to a neutralino LSP, 2. thermal saxion production and production via coherent oscillations along with cascade decays and entropy injection, 3. thermal neutralino production and re-annihilation after both axino and saxion decays, 4. gravitino production and decay and 5. axion production both thermally and via oscillations. For SUSY models with too high a standard neutralino thermal abundance, we find the combined effect of SUSY PQ particles is not enough to lower the neutralino abundance down to its measured value, while at the same time respecting bounds on late-decaying neutral particles from BBN. However, models with a standard neutralino underabundance can now be allowed with either neutralino or axion domination of dark matter, and furthermore, these models can allow the PQ breaking scale f(a) to be pushed up into the 10(14) - 10(15) GeV range, which is where it is typically expected to be in string theory models.

Encapsulation of small magnetic clusters in fullerene cages: A density functional theory investigation within van der Waals corrections

The encapsulation of magnetic transition-metal (TM) clusters inside carbon cages (fullerenes, nanotubes) has been of great interest due to the wide range of applications, which spread from medical sensors in magnetic resonance imaging to photonic crystals. Several theoretical studies have been reported; however, our atomistic understanding of the physical properties of encapsulated magnetic TM 3d clusters is far from satisfactory. In this work, we will report general trends, derived from density functional theory within the generalized gradient approximation proposed by Perdew, Burke, and Ernzerhof (PBE), for the encapsulation properties of the TMm@C-n (TM = Fe, Co, Ni; m = 2-6, n = 60,70,80,90) systems. Furthermore, to understand the role of the van der Waals corrections to the physical properties, we employed the empirical Grimme's correction (PBE + D2). We found that both PBE and PBE + D2 functionals yield almost the same geometric parameters, magnetic and electronic properties, however, PBE + D2 strongly enhances the encapsulation energy. We found that the center of mass of the TMm clusters is displaced towards the inside C-n surfaces, except for large TMm clusters (m = 5 and 6). For few cases, e. g., Co-4 and Fe-4, the encapsulation changes the putative lowest-energy structure compared to the isolated TMm clusters. We identified few physical parameters that play an important role in the sign and magnitude of the encapsulation energy, namely, cluster size, fullerene equatorial diameter, shape, curvature of the inside C-n surface, number of TM atoms that bind directly to the inside C-n surface, and the van der Waals correction. The total magnetic moment of encapsulated TMm clusters decreases compared with the isolated TMm clusters, which is expected due to the hybridization of the d-p states, and strongly depends on the size and shape of the fullerene cages.

Ethanol and Water Adsorption on Close-Packed 3d, 4d, and 5d Transition-Metal Surfaces: A Density Functional Theory Investigation with van der Waals Correction

Nowadays, there is a great interest in the economic success of direct ethanol fuel cells; however, our atomistic understanding of the designing of stable and low-cost catalysts for the steam reforming of ethanol is still far from satisfactory, in particular due to the large number of undesirable intermediates. In this study, we will report a first-principles investigation of the adsorption properties of ethanol and water at low coverage on close-packed transition-metal (TM) surfaces, namely, Fe(110), Co(0001), Ni(111), Cu(111), Ru(0001), Rh(111), Pd(111), Ag(111), Os(0001), Ir(111), Pt(111), and Au(111), employing density functional theory (DFT) calculations. We employed the generalized gradient approximation with the formulation proposed by Perdew, Burke, and Erzenholf (PBE) to the exchange correlation functional and the empirical correction proposed by S. Grimme (DFT+D3) for the van der Waals correction. We found that both adsorbates binds preferentially near or on the on top sites of the TM surfaces through the 0 atoms. The PBE adsorption energies of ethanol and water decreases almost linearly with the increased occupation of the 4d and 5d d-band, while there is a deviation for the 3d systems. The van der Waals correction affects the linear behavior and increases the adsorption energy for both adsorbates, which is expected as the van der Waals energy due to the correlation effects is strongly underestimated by DFT-PBE for weak interacting systems. The geometric parameters for water/TM are not affected by the van der Waals correction, i.e., both DFT and DFT+D3 yield an almost parallel orientation for water on the TM surfaces; however, DFT+D3 changes drastically the ethanol orientation. For example, DFT yields an almost perpendicular orientation of the C-C bond to the TM surface, while the C-C bond is almost parallel to the surface using DFT +D3 for all systems, except for ethanol/Fe(110). Thus, the van der Waals correction decreases the distance of the C atoms to the TM surfaces, which might contribute to break the C-C bond. The work function decreases upon the adsorption of ethanol and water, and both follow the same trends, however, with different magnitude (larger for ethanol/TM) due to the weak binding of water to the surface. The electron density increases mainly in the region between the topmost layer and the adsorbates, which explains the reduction of the substrate work function.

Adsorption of NO on the Rh-13, Pd-13, Ir-13, and Pt-13 Clusters: A Density Functional Theory Investigation

The adsorption of NO on transition-metal (TM) surfaces has been widely studied by experimental and theoretical techniques; however, our atomistic understanding of the interaction of nitrogen monoxide (NO) with small TM clusters is far from satisfactory, which compromises a deep understanding of real catalyst devices. In this study, we report a density functional theory study of the adsorption properties of NO on the TM13 (TM = Rh, Pd, Ir, Pt) clusters employing the projected augmented wave method. We found that the interaction of NO with TM13 is much more complex than that for NO/TM(111). In particular, for low symmetry TM13 clusters, there is a strong rearrangement of the electronic charge density upon NO adsorption and, as a consequence, the adsorption energy shows a very complex dependence even for adsorption sites with the same local effective coordination. We found a strong enhancement of the binding energy of NO to the TM13 clusters compared with the TM(111) surfaces, as the antibonding NO states are not occupied for NO/TM13, and the general relationship based on the d-band model between adsorption energy and the center of gravity of the occupied d-states does not hold for the studied TM13 clusters, in particular, for clusters with low symmetry. In contrast with the adsorption energy trends, the geometric NO/TM13 parameters and the vibrational N-O frequencies for different coordination sites follow the same trend as for the respective TM(111) surfaces, while the changes in the frequencies between different surfaces and TM13 clusters reflect the strong NO-TM13 interaction.

Platinum-Based Nanoalloys PtnTM55-n (TM=Co, Rh, Au): A Density Functional Theory Investigation

Structural and electronic properties of the PtnTM55-n (TM = Co, Rh, Au) nanoalloys are investigated using density functional theory within the generalized gradient approximation and employing the all-electron projected augmented wave method. For TM = Co and Rh, the excess energy, which measures the relative energy stability of the nanoalloys, is negative for all Pt compositions. We found that the excess energy has similar values for a wide range of Pt compositions, i.e., n = 20-42 and n = 28-42 for Co and Rh, respectively, with the core shell icosahedron-like configuration (n = 42) being slightly more stable for both Co and Rh systems because of the larger release of the strain energy due to the smaller atomic size of the Co and Rh atoms. For TM = Au, the excess energy is positive for all compositions, except for n = 13, which is energetically favorable due to the formation of the core-shell structure (Pt in the core and Au atoms at the surface). Thus, our calculations confirm that the formation of core-shell structures plays an important role to increase the stability of nanoalloys. The center of gravity of the occupied d-states changes almost linearly as a function of the Pt composition, and hence, based on the d-band model, the magnitude of the adsorption energy of an adsorbate can be tuned by changing the Pt composition. The magnetic moments of PtnCo55-n decrease almost linearly as a function of the Pt composition; however, the same does not hold for PtRh and PtAu. We found an enhancement of the magnetic moments of PtRh by a few times by increasing Pt composition, which we explain by the compression effects induced by the large size of the Pt atoms compared with the Rh atoms.

Theoretical and experimental study of the excitonic binding energy in GaAs/AlGaAs single and coupled double quantum wells

This paper discusses the theoretical and experimental results obtained for the excitonic binding energy (Eb) in a set of single and coupled double quantum wells (SQWs and CDQWs) of GaAs/AlGaAs with different Al concentrations (Al%) and inter-well barrier thicknesses. To obtain the theoretical Eb the method proposed by Mathieu, Lefebvre and Christol (MLC) was used, which is based on the idea of fractional-dimension space, together with the approach proposed by Zhao et al., which extends the MLC method for application in CDQWs. Through magnetophotoluminescence (MPL) measurements performed at 4 K with magnetic fields ranging from 0 T to 12 T, the diamagnetic shift curves were plotted and adjusted using two expressions: one appropriate to fit the curve in the range of low intensity fields and another for the range of high intensity fields, providing the experimental Eb values. The effects of increasing the Al% and the inter-well barrier thickness on Eb are discussed. The Eb reduction when going from the SQW to the CDQW with 5 Å inter-well barrier is clearly observed experimentally for 35% Al concentration and this trend can be noticed even for concentrations as low as 25% and 15%, although the Eb variations in these latter cases are within the error bars. As the Zhao's approach is unable to describe this effect, the wave functions and the probability densities for electrons and holes were calculated, allowing us to explain this effect as being due to a decrease in the spatial superposition of the wave functions caused by the thin inter-well barrier.

Effect of resonant tunneling on exciton dynamics in coupled dot-well nanostructures

Excitonic dynamics in a hybrid dot-well system composed of InAs quantum dots (QDs) and an InGaAs quantum well (QW) is studied by means of femtosecond pump-probe reflection and continuous wave (cw) photoluminescence (PL) spectroscopy. The system is engineered to bring the QW ground exciton state into resonance with the third QD excited state. The resonant tunneling rate is varied by changing the effective barrier thickness between the QD and QW layers. This strongly affects the exciton dynamics in these hybrid structures as compared to isolated QW or QD systems. Optically measured decay times of the coupled system demonstrate dramatically different response to temperature change depending on the strength of the resonant tunneling or coupling strength. This reflects a competition between purely quantum mechanical and thermodynamical processes.

Potential vorticity conserving flows and vortex-wave interaction : the role of vertical velocity and isopycnal diffusion on plankton heterogeneity

Programa de doctorado de oceanografía

Total internal reflection fluorescence cross-correlation spectroscopy: theory and application for studying boundary slip phenomenon

I present a new experimental method called Total Internal Reflection Fluorescence Cross-Correlation Spectroscopy (TIR-FCCS). It is a method that can probe hydrodynamic flows near solid surfaces, on length scales of tens of nanometres. Fluorescent tracers flowing with the liquid are excited by evanescent light, produced by epi-illumination through the periphery of a high NA oil-immersion objective. Due to the fast decay of the evanescent wave, fluorescence only occurs for tracers in the ~100 nm proximity of the surface, thus resulting in very high normal resolution. The time-resolved fluorescence intensity signals from two laterally shifted (in flow direction) observation volumes, created by two confocal pinholes are independently measured and recorded. The cross-correlation of these signals provides important information for the tracers’ motion and thus their flow velocity. Due to the high sensitivity of the method, fluorescent species with different size, down to single dye molecules can be used as tracers. The aim of my work was to build an experimental setup for TIR-FCCS and use it to experimentally measure the shear rate and slip length of water flowing on hydrophilic and hydrophobic surfaces. However, in order to extract these parameters from the measured correlation curves a quantitative data analysis is needed. This is not straightforward task due to the complexity of the problem, which makes the derivation of analytical expressions for the correlation functions needed to fit the experimental data, impossible. Therefore in order to process and interpret the experimental results I also describe a new numerical method of data analysis of the acquired auto- and cross-correlation curves – Brownian Dynamics techniques are used to produce simulated auto- and cross-correlation functions and to fit the corresponding experimental data. I show how to combine detailed and fairly realistic theoretical modelling of the phenomena with accurate measurements of the correlation functions, in order to establish a fully quantitative method to retrieve the flow properties from the experiments. An importance-sampling Monte Carlo procedure is employed in order to fit the experiments. This provides the optimum parameter values together with their statistical error bars. The approach is well suited for both modern desktop PC machines and massively parallel computers. The latter allows making the data analysis within short computing times. I applied this method to study flow of aqueous electrolyte solution near smooth hydrophilic and hydrophobic surfaces. Generally on hydrophilic surface slip is not expected, while on hydrophobic surface some slippage may exists. Our results show that on both hydrophilic and moderately hydrophobic (contact angle ~85°) surfaces the slip length is ~10-15nm or lower, and within the limitations of the experiments and the model, indistinguishable from zero.

Critical review of coupled flux formulations for clay membranes based on nonequilibrium thermodynamics

Extensive research conducted over the past several decades has indicated that semipermeable membrane behavior (i.e., the ability of a porous medium to restrict the passage of solutes) may have a significant influence on solute migration through a wide variety of clay-rich soils, including both natural clay formations (aquitards, aquicludes) and engineered clay barriers (e.g., landfill liners and vertical cutoff walls). Restricted solute migration through clay membranes generally has been described using coupled flux formulations based on nonequilibrium (irreversible) thermodynamics. However, these formulations have differed depending on the assumptions inherent in the theoretical development, resulting in some confusion regarding the applicability of the formulations. Accordingly, a critical review of coupled flux formulations for liquid, current, and solutes through a semipermeable clay membrane under isothermal conditions is undertaken with the goals of explicitly resolving differences among the formulations and illustrating the significance of the differences from theoretical and practical perspectives. Formulations based on single-solute systems (i.e., uncharged solute), single-salt systems, and general systems containing multiple cations or anions are presented. Also, expressions relating the phenomenological coefficients in the coupled flux equations to relevant soil properties (e.g., hydraulic conductivity and effective diffusion coefficient) are summarized for each system. A major difference in the formulations is shown to exist depending on whether counter diffusion or salt diffusion is assumed. This difference between counter and salt diffusion is shown to affect the interpretation of values for the effective diffusion coefficient in a clay membrane based on previously published experimental data. Solute transport theories based on both counter and salt diffusion then are used to re-evaluate previously published column test data for the same clay membrane. The results indicate that, despite the theoretical inconsistency between the counter-diffusion assumption and the salt-diffusion conditions of the experiments, the predictive ability of solute transport theory based on the assumption of counter diffusion is not significantly different from that based on the assumption of salt diffusion, provided that the input parameters used in each theory are derived under the same assumption inherent in the theory. Nonetheless, salt-diffusion theory is fundamentally correct and, therefore, is more appropriate for problems involving salt diffusion in clay membranes. Finally, the fact that solute diffusion cannot occur in an ideal or perfect membrane is not explicitly captured in any of the theoretical expressions for total solute flux in clay membranes, but rather is generally accounted for via inclusion of an effective porosity, n(e), or a restrictive tortuosity factor, tau(r), in the formulation of Fick's first law for diffusion. Both n(e) and tau(r) have been correlated as a linear function of membrane efficiency. This linear correlation is supported theoretically by pore-scale modeling of solid-liquid interactions, but experimental support is limited. Additional data are needed to bolster the validity of the linear correlation for clay membranes. Copyright 2012 Elsevier B.V. All rights reserved.

Added mass and wave radiation damping for flow-induced rotational vibrations of skinplates of hydraulic gates

One observed vibration mode for Tainter gate skinplates involves the bending of the skinplate about a horizontal nodal line. This vibration mode can be approximated as a streamwise rotational vibration about the horizontal nodal line. Such a streamwise rotational vibration of a Tainter gate skinplate must push away water from the portion of the skinplate rotating into the reservoir and draw water toward the gate over that portion of the skinplate receding from the reservoir. The induced pressure is termed the push-and-draw pressure. In the present paper, this push-and-draw pressure is analyzed using the potential theory developed for dissipative wave radiation problems. In the initial analysis, the usual circular-arc skinplate is replaced by a vertical, flat, rigid weir plate so that theoretical calculations can be undertaken. The theoretical push-and-draw pressure is used in the derivation of the non-dimensional equation of motion of the flow-induced rotational vibrations. Non-dimensionalization of the equation of motion permits the identification of the dimensionless equivalent added mass and the wave radiation damping coefficients. Free vibration tests of a vertical, flat, rigid weir plate model, both in air and in water, were performed to measure the equivalent added mass and the wave radiation damping coefficients. Experimental results compared favorably with the theoretical predictions, thus validating the theoretical analysis of the equivalent added mass and wave radiation damping coefficients as a prediction tool for flow-induced vibrations. Subsequently, the equation of motion of an inclined circular-arc skinplate was developed by incorporating a pressure correction coefficient, which permits empirical adaptation of the results from the hydrodynamic pressure analysis of the vertical, flat, rigid weir plate. Results from in-water free vibration tests on a 1/31-scale skinplate model of the Folsom Dam Tainter gate are used to demonstrate the utility of the equivalent added mass coefficient.

Critical Review of Coupled Flux Formulations for Clay Membranes Based on Nonequilibrium Thermodynamics

Extensive research conducted over the past several decades has indicated that semipermeable membrane behavior (i.e., the ability of a porous medium to restrict the passage of solutes) may have a significant influence on solute migration through a wide variety of clay-rich soils, including both natural clay formations (aquitards, aquicludes) and engineered clay barriers (e.g., landfill liners and vertical cutoff walls). Restricted solute migration through clay membranes generally has been described using coupled flux formulations based on nonequilibrium (irreversible) thermodynamics. However, these formulations have differed depending on the assumptions inherent in the theoretical development, resulting in some confusion regarding the applicability of the formulations. Accordingly, a critical review of coupled flux formulations for liquid, current, and solutes through a semipermeable clay membrane under isothermal conditions is undertaken with the goals of explicitly resolving differences among the formulations and illustrating the significance of the differences from theoretical and practical perspectives. Formulations based on single-solute systems (i.e., uncharged solute), single-salt systems, and general systems containing multiple cations or anions are presented. Also, expressions relating the phenomenological coefficients in the coupled flux equations to relevant soil properties (e.g., hydraulic conductivity and effective diffusion coefficient) are summarized for each system. A major difference in the formulations is shown to exist depending on whether counter diffusion or salt diffusion is assumed. This difference between counter and salt diffusion is shown to affect the interpretation of values for the effective diffusion coefficient in a clay membrane based on previously published experimental data. Solute transport theories based on both counter and salt diffusion then are used to re-evaluate previously published column test data for the same clay membrane. The results indicate that, despite the theoretical inconsistency between the counter-diffusion assumption and the salt-diffusion conditions of the experiments, the predictive ability of solute transport theory based on the assumption of counter diffusion is not significantly different from that based on the assumption of salt diffusion, provided that the input parameters used in each theory are derived under the same assumption inherent in the theory. Nonetheless, salt-diffusion theory is fundamentally correct and, therefore, is more appropriate for problems involving salt diffusion in clay membranes. Finally, the fact that solute diffusion cannot occur in an ideal or perfect membrane is not explicitly captured in any of the theoretical expressions for total solute flux in clay membranes, but rather is generally accounted for via inclusion of an effective porosity, ne, or a restrictive tortuosity factor, tr, in the formulation of Fick's first law for diffusion. Both ne and tr have been correlated as a linear function of membrane efficiency. This linear correlation is supported theoretically by pore-scale modeling of solid-liquid interactions, but experimental support is limited. Additional data are needed to bolster the validity of the linear correlation for clay membranes.