980 resultados para DEPENDENT QUANTUM PROBLEMS


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Esta tese relata estudos de síntese, caracterização da estrutura e das propriedades de fotoluminescência e aplicações de nanotubos e nanobastonetes de óxidos de lantanídeos em pontas para microscopia de força atómica, catálise heterogénea e compósitos de base polimérica. Há um interesse crescente em compreender como o confinamento quântico decorrente da redução do tamanho de partícula pode influenciar a eficiência da luminescência, a dinâmica dos estados excitados, a transferência de energia e os efeitos de termalização de nanoluminóforos. Em nanocristais dopados com lantanídeos (Ln3+), e apesar da localização dos estados 4f, ocorrem efeitos de confinamento quântico via interacção com os modos vibracionais da rede. Em particular, a termalização anómala, descrita para uma variedade de nanocristais dopados com Ln3+, tem sido atribuída à ausência de modos vibracionais de menor frequência. Este nanoconfinamento pode ter impacto na dinâmica da luminescência, bem como na transferência de energia mediada por modos vibracionais e processos de upconversion. Nesta tese, relata-se o estudo deste efeito em nanotubos de Gd2O3:Eu3+. A influência de parâmetros como a concentração de európio e as condições de calcinação também foi investigada. Algumas aplicações destes óxidos de lantanídeos também foram exploradas, nomeadamente a modificação de pontas usadas em microscopia de força atómica com nanobastonetes de Gd2O3:Eu3+, lograda através de dielectroforese, técnica que não degrada a emissão de luz (rendimento quântico 0.47). As pontas modificadas são estáveis sob condições de trabalho, podendo ser aplicadas, por exemplo, em microscopia óptica de varrimento de campo próximo (SNOM). A oxidação em fase líquida do etilbenzendo foi investigada usando como catalisador nanotubos de CeO2, em presença dos oxidantes hidroperóxido de t-butilo e H2O2, e do solvente acetonitrilo, e temperaturas entre 55 e 105 ºC. Nanobastonetes de Gd2O3:Eu3+ recobertos com sílica foram preparados pelo método sol-gel. Esta cobertura resultou num aumento, quer do rendimento quântico de emissão, de 0.51 para 0.86 (excitação a 255 nm), quer dos tempos de vida,de 1.43 para 1.80 ms (excitação a 394.4 nm). A superfície dos nanotubos cobertos com sílica foi modificada com o agente de acoplamento metacrilato de 3-(trimetoxissilil)propilo que permitiu a preparação de compósitos através da subsequente polimerização in-situ do estireno por técnicas de miniemulsão e solução. ABSTRACT: This thesis reports on the synthesis, characterisation of the structure and photoluminescence properties, and applications of nanotubes and nanorods of lanthanides oxides in atomic force microscopy tips, heterogeneous catalysis and polymer-base composites. There is a growing interest in understanding how size-dependent quantum confinement affects the photoluminescence efficiency, excited-state dynamics, energy-transfer and thermalisation phenomena in nanophosphors. For lanthanide (Ln3+)-doped nanocrystals, and despite the localisation of the 4f states, confinement effects are induced mostly via electron-phonon interactions. In particular, the anomalous thermalisation reported for a handful of Ln3+-doped nanocrystals has been rationalised by the absence of lowfrequency phonon modes. This nanoconfinement may further impact on the Ln3+ luminescence dynamics, such as phonon-assisted energy transfer or upconversion processes. Here, this effect is investigated in Gd2O3:Eu3+ nanotubes. The influence of parameters such as europium concentration and calcination procedure is also studied. Some applications of these lanthanides oxides have been explored, for instance the modification of atomic force microscopy tips with photoluminescent Gd2O3:Eu3+ nanorods, using dielectrophoresis, a technique which preserves the red emission of the nanorods (quantum yield 0.47). The modified tips are stable under working conditions and may find applications in scanning near-field optical microscopy. The liquid-phase oxidation of ethylbenzene over CeO2 nanotubes has been investigated, using tert-butyl-hydroperoxide and H2O2 as the oxidising agents, and acetonitrile as the solvent, in the range 55-105 ºC. Gd2O3:Eu3+ nanorods have been coated with silica via a sol-gel approach. The silica coating increases both, the Eu3+ absolute emission quantum yields from 0.51 to 0.86 (255 nm excitation), and decay times from 1.43 to 1.80 ms (394.4 nm excitation). The silica coating was modified with 3- (trimethoxysilyl) propyl methacrylate and, subsequently, composites have been prepared by in-situ radical polymerisation of styrene via miniemulsion and solution routes.

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L'approximation adiabatique en mécanique quantique stipule que si un système quantique évolue assez lentement, alors il demeurera dans le même état propre. Récemment, une faille dans l'application de l'approximation adiabatique a été découverte. Les limites du théorème seront expliquées lors de sa dérivation. Ce mémoire à pour but d'optimiser la probabilité de se maintenir dans le même état propre connaissant le système initial, final et le temps d'évolution total. Cette contrainte sur le temps empêche le système d'être assez lent pour être adiabatique. Pour solutionner ce problème, une méthode variationnelle est utilisée. Cette méthode suppose connaître l'évolution optimale et y ajoute une petite variation. Par après, nous insérons cette variation dans l'équation de la probabilité d'être adiabatique et développons en série. Puisque la série est développée autour d'un optimum, le terme d'ordre un doit nécessairement être nul. Ceci devrait nous donner un critère sur l'évolution la plus adiabatique possible et permettre de la déterminer. Les systèmes quantiques dépendants du temps sont très complexes. Ainsi, nous commencerons par les systèmes ayant des énergies propres indépendantes du temps. Puis, les systèmes sans contrainte et avec des fonctions d'onde initiale et finale libres seront étudiés.

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Femtosecond pump/probe multiphoton ionization experiments on Na_2 molecules are performed. The dependence of the total Na^+_2 ion signal on the delay time and the intensity of the femtosecond laser pulses is studied in detail. It is observed that molecular vibrational wavepacket motion in different electronic states dominates the time dependence of the ion signal. For higher laser intensities the relative contributions from the A ^1 \summe^+_u and the 2 ^1 \produkt__g states change dramatically, indicating the increasing importance of a two-electron versus a one-electron process. For even stronger fields (10 ^12 W/ cm²) a vibrational wavepacket in the electronic ground state X ^1 \summe^+_g is formed and its dynamics is also observed in the transient Na^+_2 signal. Time-dependent quantum calculations are presented. The theoretical results agree well with the experiment.

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The motion of a vibrational wave packet in the bound A(^1 \summe^+_u) electronic state of the sodium dimer is detected in a femtosecond pump/probe molecular beam experiment. For short times harmonic motion is seen in the total ion yield of Na^+_2 as a function of delay time between the two laser pulses. The spreading of the wave packet results in the loss of the periodic variation of the ion signal. For longer delay times (47 ps) the wave packet regains its initial form which is reflected in the revival structure of the Na^+_2 signal. Time-dependent quantum calculations reproduce the measured effects.

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We present a comparison between experimental and theoretical results for pump/probe multiphoton ionizing transitions of the sodium dimer, initiated by femtosecond laser pulses. It is shown that the motion of vibrational wavepackets in two electronic states is probed simultaneously and their dynamics is reflected in the total Na^+_2 ion signal which is recorded as a function of the time delay between pump and probe pulse. The time dependent quantum calculations demonstrate that two ionization pathways leading to the same final states of the molecularion exist: one gives an oscillating contribution to the ion signal, the other yields a constant background. From additional measurements of the Na^+ -transient photofragmentation spectrum it is deduced that another ionization process leading to different final ionic states exists. The process includes the excitation of a doubly excitedbound Rydberg state. This conclusion is supported by the theoretical simulation.

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The luminescence properties of solid hydrated lanthanide squarates (Ln2(C4O4)3(H2O) x; x = 8 or 13;Ln3+ = Gd, La, Eu, Tb, Pr) are reported for temperatures down to 4.2K. The luminescence of the squarate group is observed for the Gd3+ and La3+ compounds at low temperatures (below 150K). The Pr3+ compound does not show any emission at all, not even at 4.2K. This is ascribed to the quenching of the Pr3+ emission by multiphonon relaxation and/or concentration quenching. The quantum efficiencies of the 5D0 emission of Eu3+ and of the 5D4 emission of Tb3+ in these squarate complexes are strikingly different. Whereas the Tb3+ emission shows a temperature independent quantum efficiency of 50% upon ligand excitation, the Eu3+ emission is strongly quenched, showing a temperature dependent quantum efficiency of 0.8% at 4.2K upon ligand excitation. This quenching is ascribed to the low energy position of the charge-transfer state of Eu3+ in these compounds.

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Se desarrollan varias técnicas basadas en descomposición ortogonal propia (DOP) local y proyección de tipo Galerkin para acelerar la integración numérica de problemas de evolución, de tipo parabólico, no lineales. Las ideas y métodos que se presentan conllevan un nuevo enfoque para la modelización de tipo DOP, que combina intervalos temporales cortos en que se usa un esquema numérico estándard con otros intervalos temporales en que se utilizan los sistemas de tipo Galerkin que resultan de proyectar las ecuaciones de evolución sobre la variedad lineal generada por los modos DOP, obtenidos a partir de instantáneas calculadas en los intervalos donde actúa el código numérico. La variedad DOP se construye completamente en el primer intervalo, pero solamente se actualiza en los demás intervalos según las dinámicas de la solución, aumentando de este modo la eficiencia del modelo de orden reducido resultante. Además, se aprovechan algunas propiedades asociadas a la dependencia débil de los modos DOP tanto en la variable temporal como en los posibles parámetros de que pueda depender el problema. De esta forma, se aumentan la flexibilidad y la eficiencia computacional del proceso. La aplicación de los métodos resultantes es muy prometedora, tanto en la simulación de transitorios en flujos laminares como en la construcción de diagramas de bifurcación en sistemas dependientes de parámetros. Las ideas y los algoritmos desarrollados en la tesis se ilustran en dos problemas test, la ecuación unidimensional compleja de Ginzburg-Landau y el problema bidimensional no estacionario de la cavidad. Abstract Various ideas and methods involving local proper orthogonal decomposition (POD) and Galerkin projection are presented aiming at accelerating the numerical integration of nonlinear time dependent parabolic problems. The proposed methods come from a new approach to the POD-based model reduction procedures, which combines short runs with a given numerical solver and a reduced order model constructed by expanding the solution of the problem into appropriate POD modes, which span a POD manifold, and Galerkin projecting some evolution equations onto that linear manifold. The POD manifold is completely constructed from the outset, but only updated as time proceeds according to the dynamics, which yields an adaptive and flexible procedure. In addition, some properties concerning the weak dependence of the POD modes on time and possible parameters in the problem are exploited in order to increase the flexibility and efficiency of the low dimensional model computation. Application of the developed techniques to the approximation of transients in laminar fluid flows and the simulation of attractors in bifurcation problems shows very promising results. The test problems considered to illustrate the various ideas and check the performance of the algorithms are the onedimensional complex Ginzburg-Landau equation and the two-dimensional unsteady liddriven cavity problem.

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El trabajo que ha dado lugar a esta Tesis Doctoral se enmarca en la invesitagación en células solares de banda intermedia (IBSCs, por sus siglas en inglés). Se trata de un nuevo concepto de célula solar que ofrece la posibilidad de alcanzar altas eficiencias de conversión fotovoltaica. Hasta ahora, se han demostrado de manera experimental los fundamentos de operación de las IBSCs; sin embargo, esto tan sólo has sido posible en condicines de baja temperatura. El concepto de banda intermedia (IB, por sus siglas en inglés) exige que haya desacoplamiento térmico entre la IB y las bandas de valencia y conducción (VB and CB, respectivamente, por sus siglas en inglés). Los materiales de IB actuales presentan un acoplamiento térmico demasiado fuerte entre la IB y una de las otras dos bandas, lo cual impide el correcto funcionamiento de las IBSCs a temperatura ambiente. En el caso particular de las IBSCs fabricadas con puntos cuánticos (QDs, por sus siglas en inglés) de InAs/GaAs - a día de hoy, la tecnología de IBSC más estudiada - , se produce un rápido intercambio de portadores entre la IB y la CB, por dos motivos: (1) una banda prohibida estrecha (< 0.2 eV) entre la IB y la CB, E^, y (2) la existencia de niveles electrónicos entre ellas. El motivo (1) implica, a su vez, que la máxima eficiencia alcanzable en estos dispositivos es inferior al límite teórico de la IBSC ideal, en la cual E^ = 0.71 eV. En este contexto, nuestro trabajo se centra en el estudio de IBSCs de alto gap (o banda prohibida) fabricadsas con QDs, o lo que es lo mismo, QD-IBSCs de alto gap. Hemos fabricado e investigado experimentalmente los primeros prototipos de QD-IBSC en los que se utiliza AlGaAs o InGaP para albergar QDs de InAs. En ellos demostramos une distribución de gaps mejorada con respecto al caso de InAs/GaAs. En concreto, hemos medido valores de E^ mayores que 0.4 eV. En los prototipos de InAs/AlGaAs, este incremento de E^ viene acompaado de un incremento, en más de 100 meV, de la energía de activación del escape térmico. Además, nuestros dispositivos de InAs/AlGaAs demuestran conversión a la alza de tensión; es decir, la producción de una tensión de circuito abierto mayor que la energía de los fotones (dividida por la carga del electrón) de un haz monocromático incidente, así como la preservación del voltaje a temperaura ambiente bajo iluminación de luz blanca concentrada. Asimismo, analizamos el potencial para detección infrarroja de los materiales de IB. Presentamos un nuevo concepto de fotodetector de infrarrojos, basado en la IB, que hemos llamado: fotodetector de infrarrojos activado ópticamente (OTIP, por sus siglas en inglés). Nuestro novedoso dispositivo se basa en un nuevo pricipio físico que permite que la detección de luz infrarroja sea conmutable (ON y OFF) mediante iluminación externa. Hemos fabricado un OTIP basado en QDs de InAs/AlGaAs con el que demostramos fotodetección, bajo incidencia normal, en el rango 2-6/xm, activada ópticamente por un diodoe emisor de luz de 590 nm. El estudio teórico del mecanismo de detección asistido por la IB en el OTIP nos lleva a poner en cuestión la asunción de quasi-niveles de Fermi planos en la zona de carga del espacio de una célula solar. Apoyados por simuaciones a nivel de dispositivo, demostramos y explicamos por qué esta asunción no es válida en condiciones de corto-circuito e iluminación. También llevamos a cabo estudios experimentales en QD-IBSCs de InAs/AlGaAs con la finalidad de ampliar el conocimiento sobre algunos aspectos de estos dispositivos que no han sido tratados aun. En particular, analizamos el impacto que tiene el uso de capas de disminución de campo (FDLs, por sus siglas en inglés), demostrando su eficiencia para evitar el escape por túnel de portadores desde el QD al material anfitrión. Analizamos la relación existente entre el escape por túnel y la preservación del voltaje, y proponemos las medidas de eficiencia cuántica en función de la tensión como una herramienta útil para evaluar la limitación del voltaje relacionada con el túnel en QD-IBSCs. Además, realizamos medidas de luminiscencia en función de la temperatura en muestras de InAs/GaAs y verificamos que los resltados obtenidos están en coherencia con la separación de los quasi-niveles de Fermi de la IB y la CB a baja temperatura. Con objeto de contribuir a la capacidad de fabricación y caracterización del Instituto de Energía Solar de la Universidad Politécnica de Madrid (IES-UPM), hemos participado en la instalación y puesta en marcha de un reactor de epitaxia de haz molecular (MBE, por sus siglas en inglés) y el desarrollo de un equipo de caracterización de foto y electroluminiscencia. Utilizando dicho reactor MBE, hemos crecido, y posteriormente caracterizado, la primera QD-IBSC enteramente fabricada en el IES-UPM. ABSTRACT The constituent work of this Thesis is framed in the research on intermediate band solar cells (IBSCs). This concept offers the possibility of achieving devices with high photovoltaic-conversion efficiency. Up to now, the fundamentals of operation of IBSCs have been demonstrated experimentally; however, this has only been possible at low temperatures. The intermediate band (IB) concept demands thermal decoupling between the IB and the valence and conduction bands. Stateof- the-art IB materials exhibit a too strong thermal coupling between the IB and one of the other two bands, which prevents the proper operation of IBSCs at room temperature. In the particular case of InAs/GaAs quantum-dot (QD) IBSCs - as of today, the most widely studied IBSC technology - , there exist fast thermal carrier exchange between the IB and the conduction band (CB), for two reasons: (1) a narrow (< 0.2 eV) energy gap between the IB and the CB, EL, and (2) the existence of multiple electronic levels between them. Reason (1) also implies that maximum achievable efficiency is below the theoretical limit for the ideal IBSC, in which EL = 0.71 eV. In this context, our work focuses on the study of wide-bandgap QD-IBSCs. We have fabricated and experimentally investigated the first QD-IBSC prototypes in which AlGaAs or InGaP is the host material for the InAs QDs. We demonstrate an improved bandgap distribution, compared to the InAs/GaAs case, in our wide-bandgap devices. In particular, we have measured values of EL higher than 0.4 eV. In the case of the AlGaAs prototypes, the increase in EL comes with an increase of more than 100 meV of the activation energy of the thermal carrier escape. In addition, in our InAs/AlGaAs devices, we demonstrate voltage up-conversion; i. e., the production of an open-circuit voltage larger than the photon energy (divided by the electron charge) of the incident monochromatic beam, and the achievement of voltage preservation at room temperature under concentrated white-light illumination. We also analyze the potential of an IB material for infrared detection. We present a IB-based new concept of infrared photodetector that we have called the optically triggered infrared photodetector (OTIP). Our novel device is based on a new physical principle that allows the detection of infrared light to be switched ON and OFF by means of an external light. We have fabricated an OTIP based on InAs/AlGaAs QDs with which we demonstrate normal incidence photodetection in the 2-6 /xm range optically triggered by a 590 nm light-emitting diode. The theoretical study of the IB-assisted detection mechanism in the OTIP leads us to questioning the assumption of flat quasi-Fermi levels in the space-charge region of a solar cell. Based on device simulations, we prove and explain why this assumption is not valid under short-circuit and illumination conditions. We perform new experimental studies on InAs/GaAs QD-IBSC prototypes in order to gain knowledge on yet unexplored aspects of the performance of these devices. Specifically, we analyze the impact of the use of field-damping layers, and demonstrate this technique to be efficient for avoiding tunnel carrier escape from the QDs to the host material. We analyze the relationship between tunnel escape and voltage preservation, and propose voltage-dependent quantum efficiency measurements as an useful technique for assessing the tunneling-related limitation to the voltage preservation of QD-IBSC prototypes. Moreover, we perform temperature-dependent luminescence studies on InAs/GaAs samples and verify that the results are consistent with a split of the quasi-Fermi levels for the CB and the IB at low temperature. In order to contribute to the fabrication and characterization capabilities of the Solar Energy Institute of the Universidad Polite´cnica de Madrid (IES-UPM), we have participated in the installation and start-up of an molecular beam epitaxy (MBE) reactor and the development of a photo and electroluminescence characterization set-up. Using the MBE reactor, we have manufactured and characterized the first QD-IBSC fully fabricated at the IES-UPM.

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Fluoroscopic images exhibit severe signal-dependent quantum noise, due to the reduced X-ray dose involved in image formation, that is generally modelled as Poisson-distributed. However, image gray-level transformations, commonly applied by fluoroscopic device to enhance contrast, modify the noise statistics and the relationship between image noise variance and expected pixel intensity. Image denoising is essential to improve quality of fluoroscopic images and their clinical information content. Simple average filters are commonly employed in real-time processing, but they tend to blur edges and details. An extensive comparison of advanced denoising algorithms specifically designed for both signal-dependent noise (AAS, BM3Dc, HHM, TLS) and independent additive noise (AV, BM3D, K-SVD) was presented. Simulated test images degraded by various levels of Poisson quantum noise and real clinical fluoroscopic images were considered. Typical gray-level transformations (e.g. white compression) were also applied in order to evaluate their effect on the denoising algorithms. Performances of the algorithms were evaluated in terms of peak-signal-to-noise ratio (PSNR), signal-to-noise ratio (SNR), mean square error (MSE), structural similarity index (SSIM) and computational time. On average, the filters designed for signal-dependent noise provided better image restorations than those assuming additive white Gaussian noise (AWGN). Collaborative denoising strategy was found to be the most effective in denoising of both simulated and real data, also in the presence of image gray-level transformations. White compression, by inherently reducing the greater noise variance of brighter pixels, appeared to support denoising algorithms in performing more effectively. © 2012 Elsevier Ltd. All rights reserved.

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A new continuous configuration time-dependent self-consistent field method has been developed to study polyatomic dynamical problems by using the discrete variable representation for the reaction system, and applied to a reaction system coupled to a bath. The method is very efficient because the equations involved are as simple as those in the traditional single configuration approach, and can account for the correlations between the reaction system and bath modes rather well. (C) American Institute of Physics.

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We consider the two-parameter Sturm–Liouville system $$ -y_1''+q_1y_1=(\lambda r_{11}+\mu r_{12})y_1\quad\text{on }[0,1], $$ with the boundary conditions $$ \frac{y_1'(0)}{y_1(0)}=\cot\alpha_1\quad\text{and}\quad\frac{y_1'(1)}{y_1(1)}=\frac{a_1\lambda+b_1}{c_1\lambda+d_1}, $$ and $$ -y_2''+q_2y_2=(\lambda r_{21}+\mu r_{22})y_2\quad\text{on }[0,1], $$ with the boundary conditions $$ \frac{y_2'(0)}{y_2(0)} =\cot\alpha_2\quad\text{and}\quad\frac{y_2'(1)}{y_2(1)}=\frac{a_2\mu+b_2}{c_2\mu+d_2}, $$ subject to the uniform-left-definite and uniform-ellipticity conditions; where $q_{i}$ and $r_{ij}$ are continuous real valued functions on $[0,1]$, the angle $\alpha_{i}$ is in $[0,\pi)$ and $a_{i}$, $b_{i}$, $c_{i}$, $d_{i}$ are real numbers with $\delta_{i}=a_{i}d_{i}-b_{i}c_{i}>0$ and $c_{i}\neq0$ for $i,j=1,2$. Results are given on asymptotics, oscillation of eigenfunctions and location of eigenvalues.

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We study a system of ordinary differential equations linked by parameters and subject to boundary conditions depending on parameters. We assume certain definiteness conditions on the coefficient functions and on the boundary conditions that yield, in the corresponding abstract setting, a right-definite case. We give results on location of the eigenvalues and oscillation of the eigenfunctions.

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Size and strain rate effects are among several factors which play an important role in determining the response of nanostructures, such as their deformations, to the mechanical loadings. The mechanical deformations in nanostructure systems at finite temperatures are intrinsically dynamic processes. Most of the recent works in this context have been focused on nanowires [1, 2], but very little attention has been paid to such low dimensional nanostructures as quantum dots (QDs). In this contribution, molecular dynamics (MD) simulations with an embedded atom potential method(EAM) are carried out to analyse the size and strain rate effects in the silicon (Si) QDs, as an example. We consider various geometries of QDs such as spherical, cylindrical and cubic. We choose Si QDs as an example due to their major applications in solar cells and biosensing. The analysis has also been focused on the variation in the deformation mechanisms with the size and strain rate for Si QD embedded in a matrix of SiO2 [3] (other cases include SiN and SiC matrices).It is observed that the mechanical properties are the functions of the QD size, shape and strain rate as it is in the case for nanowires [2]. We also present the comparative study resulted from the application of different EAM potentials in particular, the Stillinger-Weber (SW) potential, the Tersoff potentials and the environment-dependent interatomic potential (EDIP) [1]. Finally, based on the stabilized structural properties we compute electronic bandstructures of our nanostructures using an envelope function approach and its finite element implementation.

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InN quantum dots (QDs) were grown on Si (111) by epitaxial Stranski-Krastanow growth mode using plasma-assisted molecular beam epitaxy. Single-crystalline wurtzite structure of InN QDs was verified by the x-ray diffraction and transmission electron microscopy. Scanning tunneling microscopy has been used to probe the structural aspects of QDs. A surface bandgap of InN QDs was estimated from scanning tunneling spectroscopy (STS) I-V curves and found that it is strongly dependent on the size of QDs. The observed size-dependent STS bandgap energy shifts with diameter and height were theoretical explained based on an effective mass approximation with finite-depth square-well potential model.

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We study the time-dependent transitions of a quantum-forced harmonic oscillator in noncommutative R(1,1) perturbatively to linear order in the noncommutativity theta. We show that the Poisson distribution gets modified, and that the vacuum state evolves into a `squeezed' state rather than a coherent state. The time evolutions of uncertainties in position and momentum in vacuum are also studied and imply interesting consequences for modeling nonlinear phenomena in quantum optics.