Exciton-Plasmon States in Nanoscale Materials: Breakdown of the Tamm-Dancoff Approximation

Within the Tamm-Dancoff approximation, ab initio approaches describe excitons as packets of electron-hole pairs propagating only forward in time. However, we show that in nanoscale materials excitons and plasmons hybridize, creating exciton-plasmon states where the electron-hole pairs oscillate back and forth in time. Then, as exemplified by the trans-azobenzene molecule and the carbon nanotubes, the Tamm-Dancoff approximation yields errors larger than the accuracy claimed in ab initio calculations. Instead, we propose a general and efficient approach that avoids the Tamm-Dancoff approximation, correctly describes excitons, plasmons, and exciton-plasmon states, and provides a good agreement with experimental results.

Exchange potential from the common energy denominator approximation for the Kohn-Sham Green's function: Application to (hyper)polarizabilities of molecular chains

An approximate Kohn-Sham (KS) exchange potential v(xsigma)(CEDA) is developed, based on the common energy denominator approximation (CEDA) for the static orbital Green's function, which preserves the essential structure of the density response function. v(xsigma)(CEDA) is an explicit functional of the occupied KS orbitals, which has the Slater v(Ssigma) and response v(respsigma)(CEDA) potentials as its components. The latter exhibits the characteristic step structure with "diagonal" contributions from the orbital densities \psi(isigma)\(2), as well as "off-diagonal" ones from the occupied-occupied orbital products psi(isigma)psi(j(not equal1)sigma). Comparison of the results of atomic and molecular ground-state CEDA calculations with those of the Krieger-Li-Iafrate (KLI), exact exchange (EXX), and Hartree-Fock (HF) methods show, that both KLI and CEDA potentials can be considered as very good analytical "closure approximations" to the exact KS exchange potential. The total CEDA and KLI energies nearly coincide with the EXX ones and the corresponding orbital energies epsilon(isigma) are rather close to each other for the light atoms and small molecules considered. The CEDA, KLI, EXX-epsilon(isigma) values provide the qualitatively correct order of ionizations and they give an estimate of VIPs comparable to that of the HF Koopmans' theorem. However, the additional off-diagonal orbital structure of v(xsigma)(CEDA) appears to be essential for the calculated response properties of molecular chains. KLI already considerably improves the calculated (hyper)polarizabilities of the prototype hydrogen chains H-n over local density approximation (LDA) and standard generalized gradient approximations (GGAs), while the CEDA results are definitely an improvement over the KLI ones. The reasons of this success are the specific orbital structures of the CEDA and KLI response potentials, which produce in an external field an ultranonlocal field-counteracting exchange potential. (C) 2002 American Institute of Physics.

A Wavelet Approach to the Selective Computation of Eigenvalues for Small Signal Stability Analysis

This paper proposes a method to assess the small signal stability of a power system network by selective determination of the modal eigenvalues. This uses an accelerating polynomial transform, designed using approximate eigenvalues
obtained from a wavelet approximation. Application to the IEEE 14 bus network model produced computational savings of 20%,over the QR algorithm.

Finite domination and Novikov rings: Laurent polynomial rings in two variables

Let C be a bounded cochain complex of finitely generatedfree modules over the Laurent polynomial ring L = R[x, x−1, y, y−1].The complex C is called R-finitely dominated if it is homotopy equivalentover R to a bounded complex of finitely generated projective Rmodules.Our main result characterises R-finitely dominated complexesin terms of Novikov cohomology: C is R-finitely dominated if andonly if eight complexes derived from C are acyclic; these complexes areC ⊗L R[[x, y]][(xy)−1] and C ⊗L R[x, x−1][[y]][y−1], and their variants obtainedby swapping x and y, and replacing either indeterminate by its inverse.

New Complexity Results for MAP in Bayesian Networks

This paper presents new results for the (partial) maximum a posteriori (MAP) problem in Bayesian networks, which is the problem of querying the most probable state configuration of some of the network variables given evidence. It is demonstrated that the problem remains hard even in networks with very simple topology, such as binary polytrees and simple trees (including the Naive Bayes structure), which extends previous complexity results. Furthermore, a Fully Polynomial Time Approximation Scheme for MAP in networks with bounded treewidth and bounded number of states per variable is developed. Approximation schemes were thought to be impossible, but here it is shown otherwise under the assumptions just mentioned, which are adopted in most applications.

Solving Limited Memory Influence Diagrams

We present a new algorithm for exactly solving decision making problems represented as influence diagrams. We do not require the usual assumptions of no forgetting and regularity; this allows us to solve problems with simultaneous decisions and limited information. The algorithm is empirically shown to outperform a state-of-the-art algorithm on randomly generated problems of up to 150 variables and 10^64 solutions. We show that the problem is NP-hard even if the underlying graph structure of the problem has small treewidth and the variables take on a bounded number of states, but that a fully polynomial time approximation scheme exists for these cases. Moreover, we show that the bound on the number of states is a necessary condition for any efficient approximation scheme.

The Complexity of Approximately Solving Influence Diagrams

Influence diagrams allow for intuitive and yet precise description of complex situations involving decision making under uncertainty. Unfortunately, most of the problems described by influence diagrams are hard to solve. In this paper we discuss the complexity of approximately solving influence diagrams. We do not assume no-forgetting or regularity, which makes the class of problems we address very broad. Remarkably, we show that when both the treewidth and the cardinality of the variables are bounded the problem admits a fully polynomial-time approximation scheme.

New Results for the MAP Problem in Bayesian Networks

This paper presents new results for the (partial) maximum a posteriori (MAP) problem in Bayesian networks, which is the problem of querying the most probable state configuration of some of the network variables given evidence. First, it is demonstrated that the problem remains hard even in networks with very simple topology, such as binary polytrees and simple trees (including the Naive Bayes structure). Such proofs extend previous complexity results for the problem. Inapproximability results are also derived in the case of trees if the number of states per variable is not bounded. Although the problem is shown to be hard and inapproximable even in very simple scenarios, a new exact algorithm is described that is empirically fast in networks of bounded treewidth and bounded number of states per variable. The same algorithm is used as basis of a Fully Polynomial Time Approximation Scheme for MAP under such assumptions. Approximation schemes were generally thought to be impossible for this problem, but we show otherwise for classes of networks that are important in practice. The algorithms are extensively tested using some well-known networks as well as random generated cases to show their effectiveness.

Finite domination and Novikov rings. Laurent polynomial rings in several variables

We present a homological characterisation of those chain complexes of modules over a Laurent polynomial ring in several indeterminates which are finitely dominated over the ground ring (that is, are a retract up to homotopy of a bounded complex of finitely generated free modules). The main tools, which we develop in the paper, are a non-standard totalisation construction for multi-complexes based on truncated products, and a high-dimensional mapping torus construction employing a theory of cubical diagrams that commute up to specified coherent homotopies.

Communicating ASP and the Polynomial Hierarchy

Communicating answer set programming is a framework to represent and reason about the combined knowledge of multiple agents using the idea of stable models. The semantics and expressiveness of this framework crucially depends on the nature of the communication mechanism that is adopted. The communication mechanism we introduce in this paper allows us to focus on a sequence of programs, where each program in the sequence may successively eliminate some of the remaining models. The underlying intuition is that of leaders and followers: each agent’s decisions are limited by what its leaders have previously decided. We show that extending answer set programs in this way allows us to capture the entire polynomial hierarchy.

Polynomial Model for High-Order and Multi-Carrier Passive Intermodulation Products

Passive intermodulation (PIM) often limits the performance of communication systems, particularly in the presence of multiple carriers. Since the origins of the apparently multiple physical sources of nonlinearity causing PIM in distributed circuits are not fully understood, the behavioural models are frequently employed to describe the process of PIM generation. In this paper, a memoryless nonlinear polynomial model, capable of predicting high-order multi-carrier intermodulation products, is deduced from the third-order two-tone PIM measurements on a microstrip transmission line with distributed nonlinearity. The analytical model of passive distributed nonlinearity is implemented in Keysight Technology’s ADS simulator to evaluate the adjacent band power ratio for three-tone signals. The obtained results suggest that the costly multi-carrier test setups can possibly be replaced by a simulation tool based on the properly retrieved nonlinear polynomial model.

A study of singular integral operators with shift

Nesta tese, consideram-se operadores integrais singulares com a acção extra de um operador de deslocacamento de Carleman e com coeficientes em diferentes classes de funções essencialmente limitadas. Nomeadamente, funções contínuas por troços, funções quase-periódicas e funções possuíndo factorização generalizada. Nos casos dos operadores integrais singulares com deslocamento dado pelo operador de reflexão ou pelo operador de salto no círculo unitário complexo, obtêm-se critérios para a propriedade de Fredholm. Para os coeficientes contínuos, uma fórmula do índice de Fredholm é apresentada. Estes resultados são consequência das relações de equivalência explícitas entre aqueles operadores e alguns operadores adicionais, tais como o operador integral singular, operadores de Toeplitz e operadores de Toeplitz mais Hankel. Além disso, as relações de equivalência permitem-nos obter um critério de invertibilidade e fórmulas para os inversos laterais dos operadores iniciais com coeficientes factorizáveis. Adicionalmente, aplicamos técnicas de análise numérica, tais como métodos de colocação de polinómios, para o estudo da dimensão do núcleo dos dois tipos de operadores integrais singulares com coeficientes contínuos por troços. Esta abordagem permite também a computação do inverso no sentido Moore-Penrose dos operadores principais. Para operadores integrais singulares com operadores de deslocamento do tipo Carleman preservando a orientação e com funções contínuas como coeficientes, são obtidos limites superiores da dimensão do núcleo. Tal é implementado utilizando algumas estimativas e com a ajuda de relações (explícitas) de equivalência entre operadores. Focamos ainda a nossa atenção na resolução e nas soluções de uma classe de equações integrais singulares com deslocamento que não pode ser reduzida a um problema de valor de fronteira binomial. De forma a atingir os objectivos propostos, foram utilizadas projecções complementares e identidades entre operadores. Desta forma, as equações em estudo são associadas a sistemas de equações integrais singulares. Estes sistemas são depois analisados utilizando um problema de valor de fronteira de Riemann. Este procedimento tem como consequência a construção das soluções das equações iniciais a partir das soluções de problemas de valor de fronteira de Riemann. Motivados por uma grande diversidade de aplicações, estendemos a definição de operador integral de Cauchy para espaços de Lebesgue sobre grupos topológicos. Assim, são investigadas as condições de invertibilidade dos operadores integrais neste contexto.

Optimal approximation of fractional derivatives through discrete-time fractions using genetic algorithms

This study addresses the optimization of rational fraction approximations for the discrete-time calculation of fractional derivatives. The article starts by analyzing the standard techniques based on Taylor series and Padé expansions. In a second phase the paper re-evaluates the problem in an optimization perspective by tacking advantage of the flexibility of the genetic algorithms.

Molecular simulation of gas adsorption equilibria in nanoporous materials

This work is divided into two distinct parts. The first part consists of the study of the metal organic framework UiO-66Zr, where the aim was to determine the force field that best describes the adsorption equilibrium properties of two different gases, methane and carbon dioxide. The other part of the work focuses on the study of the single wall carbon nanotube topology for ethane adsorption; the aim was to simplify as much as possible the solid-fluid force field model to increase the computational efficiency of the Monte Carlo simulations. The choice of both adsorbents relies on their potential use in adsorption processes, such as the capture and storage of carbon dioxide, natural gas storage, separation of components of biogas, and olefin/paraffin separations. The adsorption studies on the two porous materials were performed by molecular simulation using the grand canonical Monte Carlo (μ,V,T) method, over the temperature range of 298-343 K and pressure range 0.06-70 bar. The calibration curves of pressure and density as a function of chemical potential and temperature for the three adsorbates under study, were obtained Monte Carlo simulation in the canonical ensemble (N,V,T); polynomial fit and interpolation of the obtained data allowed to determine the pressure and gas density at any chemical potential. The adsorption equilibria of methane and carbon dioxide in UiO-66Zr were simulated and compared with the experimental data obtained by Jasmina H. Cavka et al. The results show that the best force field for both gases is a chargeless united-atom force field based on the TraPPE model. Using this validated force field it was possible to estimate the isosteric heats of adsorption and the Henry constants. In the Grand-Canonical Monte Carlo simulations of carbon nanotubes, we conclude that the fastest type of run is obtained with a force field that approximates the nanotube as a smooth cylinder; this approximation gives execution times that are 1.6 times faster than the typical atomistic runs.