Theoretical studies of novel organic systems : biradicals, polyradicals, and conducting polymers

Chapter 1

Cyclobutanediyl has been studied in both its singlet and triplet states by ab initio electronic structure theory. The triplet, which is the ground state of the molecule, exists in both C_(2h) and C_(2v) forms, which interconvert via a C_s transition state. For the singlet, only a C_(2h) form is found. It passes, via a C_s transition state, onto the C_(2v) surface on which bicyclobutane is the only minimum. The ring-flipping (inversion) process in bicyclobutane includes the singlet biradical as an intermediate, and involves a novel, nonleast motion pathway. Semiclassical periodic orbit theory indicates that the various minima on both the singlet and triplet surfaces can interconvert via quantum mechanical tunneling.

Chapter 2

The dimethylenepolycyclobutadienes (n) are the non-Kekulé analogues of the classical acenes. Application of a variety of theoretical methods reveals several novel features of such structures. Most interesting is the emergence of a parity rule. When n is even, n is predicted to be a singlet, with n disjoint NBMOs. When n is odd, theory predicts a triplet ground state with (n+1) NBMOs that are not fully disjoint.

Chapter 3

Bi(cyclobutadienyl) (2), the cyclobutadiene analogue of biphenyl, and its homologues tri- (3) and tetra(cyclobutadienyl) (4) have been studied using electronic structure theory. Ab initio calculations on 2 reveal that the central bond is a true double bond, and that the structure is best thought of as two allyl radicals plus an ethylene. The singlet and triplet states are essentially degenerate. Trimer 3 is two allyls plus a dimethylenecyclobutanediyl, while 4 is two coplanar bi(cyclobutadienyl) units connected by a single bond. For both 3 and 4, the quintet, triplet, and singlet states are essentially degenerate, indicating that they are tetraradicals. The infinite polymer, polycyclobutadiene, has been studied by HMO, EHCO, and VEH methods. Several geometries based on the structures of 3 and 4 have been studied, and the band structures are quite intriguing. A novel crossing between the valence and conduction bands produces a small band gap and a high density of states at the Fermi level.

Chapter 4

At the level of Hückel theory, polyfulvene has a HOCO-LUCO degeneracy much like that seen in polyacetylene. Higher levels of theory remove the degeneracy, but the band gap (E_g) is predicted to be significantly smaller than analogous structures such as polythiophene and polypyrrole at the fulvenoid geometry. An alternative geometry, which we have termed quinoid, is also conceivable for polyfulvene, and it is predicted to have a much larger E_g. The effects of benzannelation to produce analogues of polyisothianaphthene have been evaluated. We propose a new model for such structures based on conventional orbital mixing arguments. Several of the proposed structures have quite interesting properties, which suggest that they are excellent candidates for conducting polymers.

Chapter 5

Theoretical studies of polydimethylenecyclobutene and polydiisopropylidene- cyclobutene reveal that, because of steric crowding, they cannot achieve a planar, fully conjugated structure in either their undoped or doped states. Rather, the structure consists of essentially orthogonal hexatriene units. Such a structure is incompatible with conventional conduction mechanisms involving polarons and bipolarons.

Electronic states in disordered topological insulators

We present a theoretical study of electronic states in topological insulators with impurities. Chiral edge states in 2d topological insulators and helical surface states in 3d topological insulators show a robust transport against nonmagnetic impurities. Such a nontrivial character inspired physicists to come up with applications such as spintronic devices [1], thermoelectric materials [2], photovoltaics [3], and quantum computation [4]. Not only has it provided new opportunities from a practical point of view, but its theoretical study has deepened the understanding of the topological nature of condensed matter systems. However, experimental realizations of topological insulators have been challenging. For example, a 2d topological insulator fabricated in a HeTe quantum well structure by Konig et al. [5] shows a longitudinal conductance which is not well quantized and varies with temperature. 3d topological insulators such as Bi₂Se₃ and Bi₂Te₃ exhibit not only a signature of surface states, but they also show a bulk conduction [6]. The series of experiments motivated us to study the effects of impurities and coexisting bulk Fermi surface in topological insulators. We first address a single impurity problem in a topological insulator using a semiclassical approach. Then we study the conductance behavior of a disordered topological-metal strip where bulk modes are associated with the transport of edge modes via impurity scattering. We verify that the conduction through a chiral edge channel retains its topological signature, and we discovered that the transmission can be succinctly expressed in a closed form as a ratio of determinants of the bulk Green's function and impurity potentials. We further study the transport of 1d systems which can be decomposed in terms of chiral modes. Lastly, the surface impurity effect on the local density of surface states over layers into the bulk is studied between weak and strong disorder strength limits.

拉曼喷泉原子钟

利用拉曼光场代替喷泉原子钟的微波腔实现拉曼喷泉原子钟。将分离拉曼光场技术与冷原子喷泉技术相结合,避免了在真空腔内放置微波腔,简化了真空系统,同时还保持了很高的准确度。采用半经典理论研究了冷原子喷泉与拉曼光场的相互作用过程,得到了冉赛(Ramsey)条纹。比较了拉曼喷泉原子钟与热铯束拉曼原子钟,前者有更小的体积和功耗,其精度可能达到或超过商用小铯钟。还比较了拉曼喷泉原子钟与微波喷泉原子钟的差别,分析了光子反冲的影响,提出利用同向传播和相向传播的两台拉曼原子钟测量精细结构常数。

Origin of the double-peak structure in longitudinal momentum distributions for single ionization of an He atom in strong laser field

The single ionization of an He atom by intense linearly polarized laser field in the tunneling regime is studied by S- matrix theory. When only the first term of the expansion of the S matrix is considered and time, spatial distribution, and fluctuation of the laser pulse are taken into account, the obtained momentum distribution in the polarization direction of laser field is consistent with the semiclassical calculation, which only considers tunneling and the interaction between the free electron and external field. When the second term, which includes the interaction between the core and the free electron, is considered, the momentum distribution shows a complex multipeak structure with the central minimum and the positions of some peaks are independent of the intensity in some intensity regime, which is consistent with the recent experimental result. Based on our analysis, we found that the structures observed in the momentum distribution of an He atom are attributed to the " soft" collision of the tunneled electron with the core.

Lock Acquisition and Sensitivity Analysis of Advanced LIGO Interferometers

Laser interferometer gravitational wave observatory (LIGO) consists of two complex large-scale laser interferometers designed for direct detection of gravitational waves from distant astrophysical sources in the frequency range 10Hz - 5kHz. Direct detection of space-time ripples will support Einstein's general theory of relativity and provide invaluable information and new insight into physics of the Universe.

Initial phase of LIGO started in 2002, and since then data was collected during six science runs. Instrument sensitivity was improving from run to run due to the effort of commissioning team. Initial LIGO has reached designed sensitivity during the last science run, which ended in October 2010.

In parallel with commissioning and data analysis with the initial detector, LIGO group worked on research and development of the next generation detectors. Major instrument upgrade from initial to advanced LIGO started in 2010 and lasted till 2014.

This thesis describes results of commissioning work done at LIGO Livingston site from 2013 until 2015 in parallel with and after the installation of the instrument. This thesis also discusses new techniques and tools developed at the 40m prototype including adaptive filtering, estimation of quantization noise in digital filters and design of isolation kits for ground seismometers.

The first part of this thesis is devoted to the description of methods for bringing interferometer to the linear regime when collection of data becomes possible. States of longitudinal and angular controls of interferometer degrees of freedom during lock acquisition process and in low noise configuration are discussed in details.

Once interferometer is locked and transitioned to low noise regime, instrument produces astrophysics data that should be calibrated to units of meters or strain. The second part of this thesis describes online calibration technique set up in both observatories to monitor the quality of the collected data in real time. Sensitivity analysis was done to understand and eliminate noise sources of the instrument.

Coupling of noise sources to gravitational wave channel can be reduced if robust feedforward and optimal feedback control loops are implemented. The last part of this thesis describes static and adaptive feedforward noise cancellation techniques applied to Advanced LIGO interferometers and tested at the 40m prototype. Applications of optimal time domain feedback control techniques and estimators to aLIGO control loops are also discussed.

Commissioning work is still ongoing at the sites. First science run of advanced LIGO is planned for September 2015 and will last for 3-4 months. This run will be followed by a set of small instrument upgrades that will be installed on a time scale of few months. Second science run will start in spring 2016 and last for about 6 months. Since current sensitivity of advanced LIGO is already more than factor of 3 higher compared to initial detectors and keeps improving on a monthly basis, upcoming science runs have a good chance for the first direct detection of gravitational waves.

NUMERICAL STUDY OF DAMMANN ARRAY ILLUMINATORS

The numerical solutions of binary-phase (0, tau) gratings for one-dimensional array illuminators up to 32 are presented. Some fabrication errors, which are due to position-quantization errors, phase errors, dilation (or erosion) errors, and the side-slope error, are calculated and show that even-number array illuminators are superior to odd-number array illuminators when these fabrication errors are considered. One (0, tau) binary-phase, 8 x 16 array illuminator made with the wet-chemical-etching method is given in this paper.

Magnetic field and pressure effects in a saturated gas laser amplifier

Theoretical and experimental studies of a gas laser amplifier are presented, assuming the amplifier is operating with a saturating optical frequency signal. The analysis is primarily concerned with the effects of the gas pressure and the presence of an axial magnetic field on the characteristics of the amplifying medium. Semiclassical radiation theory is used, along with a density matrix description of the atomic medium which relates the motion of single atoms to the macroscopic observables. A two-level description of the atom, using phenomenological source rates and decay rates, forms the basis of our analysis of the gas laser medium. Pressure effects are taken into account to a large extent through suitable choices of decay rate parameters.

Two methods for calculating the induced polarization of the atomic medium are used. The first method utilizes a perturbation expansion which is valid for signal intensities which barely reach saturation strength, and it is quite general in applicability. The second method is valid for arbitrarily strong signals, but it yields tractable solutions only for zero magnetic field or for axial magnetic fields large enough such that the Zeeman splitting is much larger than the power broadened homogeneous linewidth of the laser transition. The effects of pressure broadening of the homogeneous spectral linewidth are included in both the weak-signal and strong-signal theories; however the effects of Zeeman sublevel-mixing collisions are taken into account only in the weak-signal theory.

The behavior of a He-Ne gas laser amplifier in the presence of an axial magnetic field has been studied experimentally by measuring gain and Faraday rotation of linearly polarized resonant laser signals for various values of input signal intensity, and by measuring nonlinearity - induced anisotropy for elliptically polarized resonant laser signals of various input intensities. Two high-gain transitions in the 3.39-μ region were used for study: a J = 1 to J = 2 (3s₂ → 3p₄) transition and a J = 1 to J = 1 (3s₂ → 3p₂) transition. The input signals were tuned to the centers of their respective resonant gain lines.

The experimental results agree quite well with corresponding theoretical expressions which have been developed to include the nonlinear effects of saturation strength signals. The experimental results clearly show saturation of Faraday rotation, and for the J = 1 t o J = 1 transition a Faraday rotation reversal and a traveling wave gain dip are seen for small values of axial magnetic field. The nonlinearity induced anisotropy shows a marked dependence on the gas pressure in the amplifier tube for the J = 1 to J = 2 transition; this dependence agrees with the predictions of the general perturbational or weak signal theory when allowances are made for the effects of Zeeman sublevel-mixing collisions. The results provide a method for measuring the upper (neon 3s₂) level quadrupole moment decay rate, the dipole moment decay rates for the 3s₂ → 3p₄ and 3s₂ → 3p₂ transitions, and the effects of various types of collision processes on these decay rates.

Uma proposta metodológica de integração de técnicas de análise espectral e de inteligência computacional, baseadas em conhecimento, para o reconhecimento de padrões em imagens multiespectrais

Somente no ano de 2011 foram adquiridos mais de 1.000TB de novos registros digitais de imagem advindos de Sensoriamento Remoto orbital. Tal gama de registros, que possui uma progressão geométrica crescente, é adicionada, anualmente, a incrível e extraordinária massa de dados de imagens orbitais já existentes da superfície da Terra (adquiridos desde a década de 70 do século passado). Esta quantidade maciça de registros, onde a grande maioria sequer foi processada, requer ferramentas computacionais que permitam o reconhecimento automático de padrões de imagem desejados, de modo a permitir a extração dos objetos geográficos e de alvos de interesse, de forma mais rápida e concisa. A proposta de tal reconhecimento ser realizado automaticamente por meio da integração de técnicas de Análise Espectral e de Inteligência Computacional com base no Conhecimento adquirido por especialista em imagem foi implementada na forma de um integrador com base nas técnicas de Redes Neurais Computacionais (ou Artificiais) (através do Mapa de Características Auto- Organizáveis de Kohonen SOFM) e de Lógica Difusa ou Fuzzy (através de Mamdani). Estas foram aplicadas às assinaturas espectrais de cada padrão de interesse, formadas pelos níveis de quantização ou níveis de cinza do respectivo padrão em cada uma das bandas espectrais, de forma que a classificação dos padrões irá depender, de forma indissociável, da correlação das assinaturas espectrais nas seis bandas do sensor, tal qual o trabalho dos especialistas em imagens. Foram utilizadas as bandas 1 a 5 e 7 do satélite LANDSAT-5 para a determinação de cinco classes/alvos de interesse da cobertura e ocupação terrestre em três recortes da área-teste, situados no Estado do Rio de Janeiro (Guaratiba, Mangaratiba e Magé) nesta integração, com confrontação dos resultados obtidos com aqueles derivados da interpretação da especialista em imagens, a qual foi corroborada através de verificação da verdade terrestre. Houve também a comparação dos resultados obtidos no integrador com dois sistemas computacionais comerciais (IDRISI Taiga e ENVI 4.8), no que tange a qualidade da classificação (índice Kappa) e tempo de resposta. O integrador, com classificações híbridas (supervisionadas e não supervisionadas) em sua implementação, provou ser eficaz no reconhecimento automático (não supervisionado) de padrões multiespectrais e no aprendizado destes padrões, pois para cada uma das entradas dos recortes da área-teste, menor foi o aprendizado necessário para sua classificação alcançar um acerto médio final de 87%, frente às classificações da especialista em imagem. A sua eficácia também foi comprovada frente aos sistemas computacionais testados, com índice Kappa médio de 0,86.

Implementação Eletrônica de Sistemas Fuzzy.

Este trabalho investiga a implementação de sistemas fuzzy com circuitos eletrônicos. Tais sistemas têm demonstrado sua capacidade de resolver diversos tipos de problemas em várias aplicações de engenharia, em especial nas relacionadas com controle de processos. Para processos mais complexos, o raciocínio aproximado da lógica fuzzy fornece uma maneira de compreender o comportamento do sistema, permitindo a interpolação aproximada entre situações observadas de entrada e saída. A implementação de um sistema fuzzy pode ser baseada em hardware, em software ou em ambos. Tipicamente, as implementações em software utilizam ambientes de programação integrados com simulação, de modo a facilitar o trabalho do projetista. As implementações em hardware, tradicionais ou evolutivas, podem ser analógicas ou digitais e viabilizam sistemas de maior desempenho. Este trabalho tem por objetivo pesquisar a implementação eletrônica de sistemas fuzzy, a fim de viabilizar a criação de sistemas reais capazes de realizar o mapeamento de entrada e saída adequado. O foco é a utilização de uma plataforma com uma arquitetura analógico-digital baseada em uma tabela de mapeamento armazenada em uma memória de alta capacidade. Memórias do tipo SD (Secure Digital) foram estudadas e utilizadas na construção do protótipo eletrônico da plataforma. Também foram desenvolvidos estudos sobre a quantização, especificamente sobre a possibilidade de redução do número de bits. Com a implementação realizada é possível desenvolver um sistema fuzzy num ambiente simulado (Matlab), configurar a plataforma e executar o sistema fuzzy diretamente na plataforma eletrônica. Os testes com o protótipo construído comprovaram seu bom funcionamento.

Spread transform watermarking for video sources

Spread Transform (ST) is a quantization watermarking algorithm in which vectors of the wavelet coefficients of a host work are quantized, using one of two dithered quantizers, to embed hidden information bits; Loo had some success in applying such a scheme to still images. We extend ST to the video watermarking problem. Visibility considerations require that each spreading vector refer to corresponding pixels in each of several frames, that is, a multi-frame embedding approach. Use of the hierarchical complex wavelet transform (CWT) for a visual mask reduces computation and improves robustness to jitter and valumetric scaling. We present a method of recovering temporal synchronization at the detector, and give initial results demonstrating the robustness and capacity of the scheme.

Nonequilibrium dynamics of photoexcited electrons in graphene: Collinear scattering, Auger processes, and the impact of screening

We present a combined analytical and numerical study of the early stages (sub-100-fs) of the nonequilibrium dynamics of photoexcited electrons in graphene. We employ the semiclassical Boltzmann equation with a collision integral that includes contributions from electron-electron (e-e) and electron-optical phonon interactions. Taking advantage of circular symmetry and employing the massless Dirac fermion (MDF) Hamiltonian, we are able to perform an essentially analytical study of the e-e contribution to the collision integral. This allows us to take particular care of subtle collinear scattering processes - processes in which incoming and outgoing momenta of the scattering particles lie on the same line - including carrier multiplication (CM) and Auger recombination (AR). These processes have a vanishing phase space for two-dimensional MDF bare bands. However, we argue that electron-lifetime effects, seen in experiments based on angle-resolved photoemission spectroscopy, provide a natural pathway to regularize this pathology, yielding a finite contribution due to CM and AR to the Coulomb collision integral. Finally, we discuss in detail the role of physics beyond the Fermi golden rule by including screening in the matrix element of the Coulomb interaction at the level of the random phase approximation (RPA), focusing in particular on the consequences of various approximations including static RPA screening, which maximizes the impact of CM and AR processes, and dynamical RPA screening, which completely suppresses them. © 2013 American Physical Society.

Magnetic quantum oscillations for the surface states of topological insulator Bi2Se3

We study quantum oscillations of the magnetization in Bi2Se3 (111) surface system in the presence of a perpendicular magnetic field. The combined spin-chiral Dirac cone and Landau quantization produce profound effects on the magnetization properties that are fundamentally different from those in the conventional semiconductor two-dimensional electron gas. In particular, we show that the oscillating center in the magnetization chooses to pick up positive or negative values depending on whether the zero-mode Landau level is occupied or empty. An intuitive analysis of these features is given and the subsequent effects on the magnetic susceptibility and Hall conductance are also discussed.

Transfer and detection of single electrons using metal-oxide-semiconductor field-effect transistors

A single-electron turnstile and electrometer circuit was fabricated on a silicon-on-insulator substrate. The turnstile, which is operated by opening and closing two metal-oxide-semiconductor field-effect transistors (MOSFETs) alternately, allows current quantization at 20 K due to single-electron transfer. Another MOSFET is placed at the drain side of the turnstile to form an electron storage island. Therefore, one-by-one electron entrance into the storage island from the turnstile can be detected as an abrupt change in the current of the electrometer, which is placed near the storage island and electrically coupled to it. The correspondence between the quantized current and the single-electron counting was confirmed.

Greatly enhanced resonant tunneling of photo-excited holes in a three-barrier resonant tunneling structure

By integrating a resonant tunneling diode with a 1.2 mu m-thick slightly doped n-type GaAs layer in a three-barrier, two-well resonant tunneling structure, the resonant tunneling of photo-excited holes exhibits a value of peak-to-valley current ratio (PVCR) as high as 36. A vast number of photo-excited holes generated in this 1.2 mu m-thick slightly doped n-type GaAs layer, and the quantization of hole levels in a 23nm-thick quantum well on the outgoing side of hole tunneling out off the resonant tunneling diode which greatly depressed the valley current of the holes, are thought to be responsible for such greatly enhanced PVCR.

Quantum mechanical effects in nanometer field effect transistors

The atomistic pseudopotential quantum mechanical calculations for million atom nanosized metal-oxide-semiconductor field-effect transistors (MOSFETs) are presented. When compared with semiclassical Thomas-Fermi simulation results, there are significant differences in I-V curve, electron threshold voltage, and gate capacitance. In many aspects, the quantum mechanical effects exacerbate the problems encountered during device minimization, and it also presents different mechanisms in controlling the behaviors of a nanometer device than the classical one. (c) 2007 American Institute of Physics.