Higher-order molecular properties and excitation energies in single-reference and multireference coupled-cluster theory

Coupled-cluster (CC) theory is one of the most successful approaches in high-accuracy quantum chemistry. The present thesis makes a number of contributions to the determination of molecular properties and excitation energies within the CC framework. The multireference CC (MRCC) method proposed by Mukherjee and coworkers (Mk-MRCC) has been benchmarked within the singles and doubles approximation (Mk-MRCCSD) for molecular equilibrium structures. It is demonstrated that Mk-MRCCSD yields reliable results for multireference cases where single-reference CC methods fail. At the same time, the present work also illustrates that Mk-MRCC still suffers from a number of theoretical problems and sometimes gives rise to results of unsatisfactory accuracy. To determine polarizability tensors and excitation spectra in the MRCC framework, the Mk-MRCC linear-response function has been derived together with the corresponding linear-response equations. Pilot applications show that Mk-MRCC linear-response theory suffers from a severe problem when applied to the calculation of dynamic properties and excitation energies: The Mk-MRCC sufficiency conditions give rise to a redundancy in the Mk-MRCC Jacobian matrix, which entails an artificial splitting of certain excited states. This finding has established a new paradigm in MRCC theory, namely that a convincing method should not only yield accurate energies, but ought to allow for the reliable calculation of dynamic properties as well. In the context of single-reference CC theory, an analytic expression for the dipole Hessian matrix, a third-order quantity relevant to infrared spectroscopy, has been derived and implemented within the CC singles and doubles approximation. The advantages of analytic derivatives over numerical differentiation schemes are demonstrated in some pilot applications.

Light-cone Wilson loop in classical lattice gauge theory

The transverse broadening of an energetic jet passing through a non-Abelian plasma is believed to be described by the thermal expectation value of a light-cone Wilson loop. In this exploratory study, we measure the light-cone Wilson loop with classical lattice gauge theory simulations. We observe, as suggested by previous studies, that there are strong interactions already at short transverse distances, which may lead to more efficient jet quenching than in leading-order perturbation theory. We also verify that the asymptotics of the Wilson loop do not change qualitatively when crossing the light cone, which supports arguments in the literature that infrared contributions to jet quenching can be studied with dimensionally reduced simulations in the space-like domain. Finally we speculate on possibilities for full four-dimensional lattice studies of the same observable, perhaps by employing shifted boundary conditions in order to simulate ensembles boosted by an imaginary velocity.

Relating Crevassing to Non-Linear Strain in the Floating Part of Jakobshavn Isbrae, West Greenland

Jakobshavn Isbrae is a major ice stream that drains the west-central Greenland ice sheet and becomes afloat in Jakobshavn Isfiord (69degreesN, 49degreesW), where it has maintained the world's fastest-known sustained velocity and calving rate (7 km a(-1)) for at least four decades. The floating portion is approximately 12 km long and 6 km wide. Surface elevations and motion vectors were determined photogrammetrically for about 500 crevasses on the floating ice, and adjacent grounded ice, using aerial photographs obtained 2 weeks apart in July 1985. Surface strain rates were computed from a mesh of 399 quadrilateral elements having velocity measurements at each corner. It is shown that heavy crevassing of floating ice invalidates the assumptions of linear strain theory that (i) surface strain in the floating ice is homogeneous in both space and time, (ii) the squares and products of strain components are nil, and (iii) first- and second-order rotation components are small compared to strain components. Therefore, strain rates and rotation rates were also computed using non-linear strain theory. The percentage difference between computed linear and non-linear second invariants of strain rate per element were greatest (mostly in the range 40-70%) where crevassing is greatest. Isopleths of strain rate parallel and transverse to flow and elevation isopleths relate crevassing to known and inferred pinning points.

Global Linear Instability at the Dawn of its 4th Decade: A List of Challenges (A Practical Guide on how to Contain the Euphoria and Avoid the Oversell)

Global linear instability theory is concerned with the temporal or spatial development of small-amplitude perturbations superposed upon laminar steady or time-periodic threedimensional flows, which are inhomogeneous in two (and periodic in one) or all three spatial directions.1 The theory addresses flows developing in complex geometries, in which the parallel or weakly nonparallel basic flow approximation invoked by classic linear stability theory does not hold. As such, global linear theory is called to fill the gap in research into stability and transition in flows over or through complex geometries. Historically, global linear instability has been (and still is) concerned with solution of multi-dimensional eigenvalue problems; the maturing of non-modal linear instability ideas in simple parallel flows during the last decade of last century2–4 has given rise to investigation of transient growth scenarios in an ever increasing variety of complex flows. After a brief exposition of the theory, connections are sought with established approaches for structure identification in flows, such as the proper orthogonal decomposition and topology theory in the laminar regime and the open areas for future research, mainly concerning turbulent and three-dimensional flows, are highlighted. Recent results obtained in our group are reported in both the time-stepping and the matrix-forming approaches to global linear theory. In the first context, progress has been made in implementing a Jacobian-Free Newton Krylov method into a standard finite-volume aerodynamic code, such that global linear instability results may now be obtained in compressible flows of aeronautical interest. In the second context a new stable very high-order finite difference method is implemented for the spatial discretization of the operators describing the spatial BiGlobal EVP, PSE-3D and the TriGlobal EVP; combined with sparse matrix treatment, all these problems may now be solved on standard desktop computers.

Four Decades of Studying Global Linear Instability: Progress and Challenges

Global linear instability theory is concerned with the temporal or spatial development of small-amplitude perturbations superposed upon laminar steady or time-periodic three-dimensional flows, which are inhomogeneous in two(and periodic in one)or all three spatial directions.After a brief exposition of the theory,some recent advances are reported. First, results are presented on the implementation of a Jacobian-free Newton–Krylov time-stepping method into a standard finite-volume aerodynamic code to obtain global linear instability results in flows of industrial interest. Second, connections are sought between established and more-modern approaches for structure identification in flows, such as proper orthogonal decomposition and Koopman modes analysis (dynamic mode decomposition), and the possibility to connect solutions of the eigenvalue problem obtained by matrix formation or time-stepping with those delivered by dynamic mode decomposition, residual algorithm, and proper orthogonal decomposition analysis is highlighted in the laminar regime; turbulent and three-dimensional flows are identified as open areas for future research. Finally, a new stable very-high-order finite-difference method is implemented for the spatial discretization of the operators describing the spatial biglobal eigenvalue problem, parabolized stability equation three-dimensional analysis, and the triglobal eigenvalue problem; it is shown that, combined with sparse matrix treatment, all these problems may now be solved on standard desktop computers

Adaptive control system based on lineal control theory for the path-following problem of a car-like mobile robot

The objective of this paper is to design a path following control system for a car-like mobile robot using classical linear control techniques, so that it adapts on-line to varying conditions during the trajectory following task. The main advantages of the proposed control structure is that well known linear control theory can be applied in calculating the PID controllers to full control requirements, while at the same time it is exible to be applied in non-linear changing conditions of the path following task. For this purpose the Frenet frame kinematic model of the robot is linearised at a varying working point that is calculated as a function of the actual velocity, the path curvature and kinematic parameters of the robot, yielding a transfer function that varies during the trajectory. The proposed controller is formed by a combination of an adaptive PID and a feed-forward controller, which varies accordingly with the working conditions and compensates the non-linearity of the system. The good features and exibility of the proposed control structure have been demonstrated through realistic simulations that include both kinematics and dynamics of the car-like robot.

Linear Sparse Differential Resultant Formulas

Let P be a system of n linear nonhomogeneous ordinary differential polynomials in a set U of n-1 differential indeterminates. Differential resultant formulas are presented to eliminate the differential indeterminates in U from P. These formulas are determinants of coefficient matrices of appropriate sets of derivatives of the differential polynomials in P, or in a linear perturbation Pe of P. In particular, the formula dfres(P) is the determinant of a matrix M(P) having no zero columns if the system P is ``super essential". As an application, if the system PP is sparse generic, such formulas can be used to compute the differential resultant dres(PP) introduced by Li, Gao and Yuan.

Magnetic Attitude Control System for a Small Satellite. Impact on the Thermal Performance

El principal objetivo de la tesis es estudiar el acoplamiento entre los subsistemas de control de actitud y de control térmico de un pequeño satélite, con el fin de buscar la solución a los problemas relacionados con la determinación de los parámetros de diseño. Se considera la evolución de la actitud y de las temperaturas del satélite bajo la influencia de dos estrategias de orientación diferentes: 1) estabilización magnética pasiva de la orientación (PMAS, passive magnetic attitude stabilization), y 2) control de actitud magnético activo (AMAC, active magnetic attitude control). En primer lugar se presenta el modelo matemático del problema, que incluye la dinámica rotacional y el modelo térmico. En el problema térmico se considera un satélite cúbico modelizado por medio de siete nodos (seis externos y uno interno) aplicando la ecuación del balance térmico. Una vez establecido el modelo matemático del problema, se estudia la evolución que corresponde a las dos estrategias mencionadas. La estrategia PMAS se ha seleccionado por su simplicidad, fiabilidad, bajo coste, ahorrando consumo de potencia, masa coste y complejidad, comparado con otras estrategias. Se ha considerado otra estrategia de control que consigue que el satélite gire a una velocidad requerida alrededor de un eje deseado de giro, pudiendo controlar su dirección en un sistema inercial de referencia, ya que frecuentemente el subsistema térmico establece requisitos de giro alrededor de un eje del satélite orientado en una dirección perpendicular a la radiación solar incidente. En relación con el problema térmico, para estudiar la influencia de la velocidad de giro en la evolución de las temperaturas en diversos puntos del satélite, se ha empleado un modelo térmico linealizado, obtenido a partir de la formulación no lineal aplicando un método de perturbaciones. El resultado del estudio muestra que el tiempo de estabilización de la temperatura y la influencia de las cargas periódicas externas disminuye cuando aumenta la velocidad de giro. Los cambios de temperatura se reducen hasta ser muy pequeños para velocidades de rotación altas. En relación con la estrategia PMAC se ha observado que a pesar de su uso extendido entre los micro y nano satélites todavía presenta problemas que resolver. Estos problemas están relacionados con el dimensionamiento de los parámetros del sistema y la predicción del funcionamiento en órbita. Los problemas aparecen debido a la dificultad en la determinación de las características magnéticas de los cuerpos ferromagnéticos (varillas de histéresis) que se utilizan como amortiguadores de oscilaciones en los satélites. Para estudiar este problema se presenta un modelo analítico que permite estimar la eficiencia del amortiguamiento, y que se ha aplicado al estudio del comportamiento en vuelo de varios satélites, y que se ha empleado para comparar los resultados del modelo con los obtenidos en vuelo, observándose que el modelo permite explicar satisfactoriamente el comportamiento registrado. ABSTRACT The main objective of this thesis is to study the coupling between the attitude control and thermal control subsystems of a small satellite, and address the solution to some existing issues concerning the determination of their parameters. Through the thesis the attitude and temperature evolution of the satellite is studied under the influence of two independent attitude stabilization and control strategies: (1) passive magnetic attitude stabilization (PMAS), and (2) active magnetic attitude control (AMAC). In this regard the mathematical model of the problem is explained and presented. The mathematical model includes both the rotational dynamics and the thermal model. The thermal model is derived for a cubic satellite by solving the heat balance equation for 6 external and 1 internal nodes. Once established the mathematical model of the problem, the above mentioned attitude strategies were applied to the system and the temperature evolution of the 7 nodes of the satellite was studied. The PMAS technique has been selected to be studied due to its prevalent use, simplicity, reliability, and cost, as this strategy significantly saves the overall power, weight, cost, and reduces the complexity of the system compared to other attitude control strategies. In addition to that, another control law that provides the satellite with a desired spin rate along a desired axis of the satellite, whose direction can be controlled with respect to the inertial reference frame is considered, as the thermal subsystem of a satellite usually demands a spin requirement around an axis of the satellite which is positioned perpendicular to the direction of the coming solar radiation. Concerning the thermal problem, to study the influence of spin rate on temperature evolution of the satellite a linear approach of the thermal model is used, which is based on perturbation theory applied to the nonlinear differential equations of the thermal model of a spacecraft moving in a closed orbit. The results of this study showed that the temperature stabilization time and the periodic influence of the external thermal loads decreases by increasing the spin rate. However, the changes become insignificant for higher values of spin rate. Concerning the PMAS strategy, it was observed that in spite of its extended application to micro and nano satellites, still there are some issues to be solved regarding this strategy. These issues are related to the sizing of its system parameters and predicting the in-orbit performance. The problems were found to be rooted in the difficulties that exist in determining the magnetic characteristics of the ferromagnetic bodies (hysteresis rods) that are applied as damping devices on-board satellites. To address these issues an analytic model for estimating their damping efficiency is proposed and applied to several existing satellites in order to compare the results with their respective in-flight data. This model can explain the behavior showed by these satellites.

V-substituted In2S3: an intermediate band material with photocatalytic activity in the whole visible light range

We proposed in our previous work V-substituted In2S3 as an intermediate band (IB) material able to enhance the efficiency of photovoltaic cells by combining two photons to achieve a higher energy electron excitation, much like natural photosynthesis. Here this hyper-doped material is tested in a photocatalytic reaction using wavelength-controlled light. The results evidence its ability to use photons with wavelengths of up to 750 nm, i.e. with energy significantly lower than the bandgap (=2.0 eV) of non-substituted In2S3, driving with them the photocatalytic reaction at rates comparable to those of non-substituted In2S3 in its photoactivity range (λ ≤ 650 nm). Photoluminescence spectra evidence that the same bandgap excitation as in V-free In2S3 occurs in V-substituted In2S3 upon illumination with photons in the same sub-bandgap energy range which is effective in photocatalysis, and its linear dependence on light intensity proves that this is not due to a nonlinear optical property. This evidences for the first time that a two-photon process can be active in photocatalysis in a single-phase material. Quantum calculations using GW-type many-body perturbation theory suggest that the new band introduced in the In2S3 gap by V insertion is located closer to the conduction band than to the valence band, so that hot carriers produced by the two-photon process would be of electron type; they also show that the absorption coefficients of both transitions involving the IB are of significant and similar magnitude. The results imply that V-substituted In2S3, besides being photocatalytically active in the whole visible light range (a property which could be used for the production of solar fuels), could make possible photovoltaic cells of improved efficiency.

Mode Localization in a Nearly Cyclic Symmetric System

Thesis (Ph.D.)--University of Washington, 2016-06

Theory of strongly correlated electron systems. I. Intersite coulomb interaction and the approximation of renormalized fermions in total energy calculations

The diagrammatic strong-coupling perturbation theory (SCPT) for correlated electron systems is developed for intersite Coulomb interaction and for a nonorthogonal basis set. The construction is based on iterations of exact closed equations for many - electron Green functions (GFs) for Hubbard operators in terms of functional derivatives with respect to external sources. The graphs, which do not contain the contributions from the fluctuations of the local population numbers of the ion states, play a special role: a one-to-one correspondence is found between the subset of such graphs for the many - electron GFs and the complete set of Feynman graphs of weak-coupling perturbation theory (WCPT) for single-electron GFs. This fact is used for formulation of the approximation of renormalized Fermions (ARF) in which the many-electron quasi-particles behave analogously to normal Fermions. Then, by analyzing: (a) Sham's equation, which connects the self-energy and the exchange- correlation potential in density functional theory (DFT); and (b) the Galitskii and Migdal expressions for the total energy, written within WCPT and within ARF SCPT, a way we suggest a method to improve the description of the systems with correlated electrons within the local density approximation (LDA) to DFT. The formulation, in terms of renormalized Fermions LIDA (RF LDA), is obtained by introducing the spectral weights of the many electron GFs into the definitions of the charge density, the overlap matrices, effective mixing and hopping matrix elements, into existing electronic structure codes, whereas the weights themselves have to be found from an additional set of equations. Compared with LDA+U and self-interaction correction (SIC) methods, RF LDA has the advantage of taking into account the transfer of spectral weights, and, when formulated in terms of GFs, also allows for consideration of excitations and nonzero temperature. Going beyond the ARF SCPT, as well as RF LIDA, and taking into account the fluctuations of ion population numbers would require writing completely new codes for ab initio calculations. The application of RF LDA for ab initio band structure calculations for rare earth metals is presented in part 11 of this study (this issue). (c) 2005 Wiley Periodicals, Inc.

Mathematical and numerical modelling of dispersion-managed solitons, autosolitons and self-similar optical pulses

This thesis presents theoretical investigation of three topics concerned with nonlinear optical pulse propagation in optical fibres. The techniques used are mathematical analysis and numerical modelling. Firstly, dispersion-managed (DM) solitons in fibre lines employing a weak dispersion map are analysed by means of a perturbation approach. In the case of small dispersion map strengths the average pulse dynamics is described by a perturbation approach (NLS) equation. Applying a perturbation theory, based on the Inverse Scattering Transform method, an analytic expression for the envelope of the DM soliton is derived. This expression correctly predicts the power enhancement arising from the dispersion management.Secondly, autosoliton transmission in DM fibre systems with periodical in-line deployment of nonlinear optical loop mirrors (NOLMs) is investigated. The use of in-line NOLMs is addressed as a general technique for all-optical passive 2R regeneration of return-to-zero data in high speed transmission system with strong dispersion management. By system optimisation, the feasibility of ultra-long single-channel and wavelength-division multiplexed data transmission at bit-rates ³ 40 Gbit s-1 in standard fibre-based systems is demonstrated. The tolerance limits of the results are defined.Thirdly, solutions of the NLS equation with gain and normal dispersion, that describes optical pulse propagation in an amplifying medium, are examined. A self-similar parabolic solution in the energy-containing core of the pulse is matched through Painlevé functions to the linear low-amplitude tails. The analysis provides a full description of the features of high-power pulses generated in an amplifying medium.

Breakup of a multisoliton state of the linearly damped nonlinear Schrödinger equation

We address the breakup (splitting) of multisoliton solutions of the nonlinear Schrödinger equation (NLSE), occurring due to linear loss. Two different approaches are used for the study of the splitting process. The first one is based on the direct numerical solution of the linearly damped NLSE and the subsequent analysis of the eigenvalue drift for the associated Zakharov-Shabat spectral problem. The second one involves the multisoliton adiabatic perturbation theory applied for studying the evolution of the solution parameters, with the linear loss taken as a small perturbation. We demonstrate that in the case of strong nonadiabatic loss the evolution of the Zakharov-Shabat eigenvalues can be quite nontrivial. We also demonstrate that the multisoliton breakup can be correctly described within the framework of the adiabatic perturbation theory and can take place even due to small linear loss. Eventually we elucidate the occurrence of the splitting and its dependence on the phase mismatch between the solitons forming a two-soliton bound state. © 2007 The American Physical Society.

Channel model and lower capacity bound for the transmission based on nonlinear Fourier transform

The integrability of the nonlinear Schräodinger equation (NLSE) by the inverse scattering transform shown in a seminal work [1] gave an interesting opportunity to treat the corresponding nonlinear channel similar to a linear one by using the nonlinear Fourier transform. Integrability of the NLSE is in the background of the old idea of eigenvalue communications [2] that was resurrected in recent works [3{7]. In [6, 7] the new method for the coherent optical transmission employing the continuous nonlinear spectral data | nonlinear inverse synthesis was introduced. It assumes the modulation and detection of data using directly the continuous part of nonlinear spectrum associated with an integrable transmission channel (the NLSE in the case considered). Although such a transmission method is inherently free from nonlinear impairments, the noisy signal corruptions, arising due to the ampli¯er spontaneous emission, inevitably degrade the optical system performance. We study properties of the noise-corrupted channel model in the nonlinear spectral domain attributed to NLSE. We derive the general stochastic equations governing the signal evolution inside the nonlinear spectral domain and elucidate the properties of the emerging nonlinear spectral noise using well-established methods of perturbation theory based on inverse scattering transform [8]. It is shown that in the presence of small noise the communication channel in the nonlinear domain is the additive Gaussian channel with memory and signal-dependent correlation matrix. We demonstrate that the effective spectral noise acquires colouring", its autocorrelation function becomes slow decaying and non-diagonal as a function of \frequencies", and the noise loses its circular symmetry, becoming elliptically polarized. Then we derive a low bound for the spectral effiency for such a channel. Our main result is that by using the nonlinear spectral techniques one can significantly increase the achievable spectral effiency compared to the currently available methods [9]. REFERENCES 1. Zakharov, V. E. and A. B. Shabat, Sov. Phys. JETP, Vol. 34, 62{69, 1972. 2. Hasegawa, A. and T. Nyu, J. Lightwave Technol., Vol. 11, 395{399, 1993. 3. Yousefi, M. I. and F. R. Kschischang, IEEE Trans. Inf. Theory, Vol. 60, 4312{4328, 2014. 4. Yousefi, M. I. and F. R. Kschischang, IEEE Trans. Inf. Theory, Vol. 60, 4329{4345 2014. 5. Yousefi, M. I. and F. R. Kschischang, IEEE Trans. Inf. Theory, Vol. 60, 4346{4369, 2014. 6. Prilepsky, J. E., S. A. Derevyanko, K. J. Blow, I. Gabitov, and S. K. Turitsyn, Phys. Rev. Lett., Vol. 113, 013901, 2014. 7. Le, S. T., J. E. Prilepsky, and S. K. Turitsyn, Opt. Express, Vol. 22, 26720{26741, 2014. 8. Kaup, D. J. and A. C. Newell, Proc. R. Soc. Lond. A, Vol. 361, 413{446, 1978. 9. Essiambre, R.-J., G. Kramer, P. J. Winzer, G. J. Foschini, and B. Goebel, J. Lightwave Technol., Vol. 28, 662{701, 2010.

Nonlinear quantum transport in low-dimensional electronic devices

The study of transport processes in low-dimensional semiconductors requires a rigorous quantum mechanical treatment. However, a full-fledged quantum transport theory of electrons (or holes) in semiconductors of small scale, applicable in the presence of external fields of arbitrary strength, is still not available. In the literature, different approaches have been proposed, including: (a) the semiclassical Boltzmann equation, (b) perturbation theory based on Keldysh's Green functions, and (c) the Quantum Boltzmann Equation (QBE), previously derived by Van Vliet and coworkers, applicable in the realm of Kubo's Linear Response Theory (LRT). ^ In the present work, we follow the method originally proposed by Van Wet in LRT. The Hamiltonian in this approach is of the form: H = H 0(E, B) + λV, where H0 contains the externally applied fields, and λV includes many-body interactions. This Hamiltonian differs from the LRT Hamiltonian, H = H0 - AF(t) + λV, which contains the external field in the field-response part, -AF(t). For the nonlinear problem, the eigenfunctions of the system Hamiltonian, H0(E, B), include the external fields without any limitation on strength. ^ In Part A of this dissertation, both the diagonal and nondiagonal Master equations are obtained after applying projection operators to the von Neumann equation for the density operator in the interaction picture, and taking the Van Hove limit, (λ → 0, t → ∞, so that (λ2 t)n remains finite). Similarly, the many-body current operator J is obtained from the Heisenberg equation of motion. ^ In Part B, the Quantum Boltzmann Equation is obtained in the occupation-number representation for an electron gas, interacting with phonons or impurities. On the one-body level, the current operator obtained in Part A leads to the Generalized Calecki current for electric and magnetic fields of arbitrary strength. Furthermore, in this part, the LRT results for the current and conductance are recovered in the limit of small electric fields. ^ In Part C, we apply the above results to the study of both linear and nonlinear longitudinal magneto-conductance in quasi one-dimensional quantum wires (1D QW). We have thus been able to quantitatively explain the experimental results, recently published by C. Brick, et al., on these novel frontier-type devices. ^