Ground and Electronic Excited States from Pairing Matrix Fluctuation and Particle-Particle Random Phase Approximation

The accurate description of ground and electronic excited states is an important and challenging topic in quantum chemistry. The pairing matrix fluctuation, as a counterpart of the density fluctuation, is applied to this topic. From the pairing matrix fluctuation, the exact electron correlation energy as well as two electron addition/removal energies can be extracted. Therefore, both ground state and excited states energies can be obtained and they are in principle exact with a complete knowledge of the pairing matrix fluctuation. In practice, considering the exact pairing matrix fluctuation is unknown, we adopt its simple approximation --- the particle-particle random phase approximation (pp-RPA) --- for ground and excited states calculations. The algorithms for accelerating the pp-RPA calculation, including spin separation, spin adaptation, as well as an iterative Davidson method, are developed. For ground states correlation descriptions, the results obtained from pp-RPA are usually comparable to and can be more accurate than those from traditional particle-hole random phase approximation (ph-RPA). For excited states, the pp-RPA is able to describe double, Rydberg, and charge transfer excitations, which are challenging for conventional time-dependent density functional theory (TDDFT). Although the pp-RPA intrinsically cannot describe those excitations excited from the orbitals below the highest occupied molecular orbital (HOMO), its performances on those single excitations that can be captured are comparable to TDDFT. The pp-RPA for excitation calculation is further applied to challenging diradical problems and is used to unveil the nature of the ground and electronic excited states of higher acenes. The pp-RPA and the corresponding Tamm-Dancoff approximation (pp-TDA) are also applied to conical intersections, an important concept in nonadiabatic dynamics. Their good description of the double-cone feature of conical intersections is in sharp contrast to the failure of TDDFT. All in all, the pairing matrix fluctuation opens up new channel of thinking for quantum chemistry, and the pp-RPA is a promising method in describing ground and electronic excited states.

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.

Theoretical Rationalization of the Singlet–Triplet Gap in OLEDs Materials: Impact of Charge-Transfer Character

New materials for OLED applications with low singlet–triplet energy splitting have been recently synthesized in order to allow for the conversion of triplet into singlet excitons (emitting light) via a Thermally Activated Delayed Fluorescence (TADF) process, which involves excited-states with a non-negligible amount of Charge-Transfer (CT). The accurate modeling of these states with Time-Dependent Density Functional Theory (TD-DFT), the most used method so far because of the favorable trade-off between accuracy and computational cost, is however particularly challenging. We carefully address this issue here by considering materials with small (high) singlet–triplet gap acting as emitter (host) in OLEDs and by comparing the accuracy of TD-DFT and the corresponding Tamm-Dancoff Approximation (TDA), which is found to greatly reduce error bars with respect to experiments thanks to better estimates for the lowest singlet–triplet transition. Finally, we quantitatively correlate the singlet–triplet splitting values with the extent of CT, using for it a simple metric extracted from calculations with double-hybrid functionals, that might be applied in further molecular engineering studies.

Iterated stochastic filters with additive updates for dynamic system identification: Annealing-type iterations and the filter bank

A nonlinear stochastic filtering scheme based on a Gaussian sum representation of the filtering density and an annealing-type iterative update, which is additive and uses an artificial diffusion parameter, is proposed. The additive nature of the update relieves the problem of weight collapse often encountered with filters employing weighted particle based empirical approximation to the filtering density. The proposed Monte Carlo filter bank conforms in structure to the parent nonlinear filtering (Kushner-Stratonovich) equation and possesses excellent mixing properties enabling adequate exploration of the phase space of the state vector. The performance of the filter bank, presently assessed against a few carefully chosen numerical examples, provide ample evidence of its remarkable performance in terms of filter convergence and estimation accuracy vis-a-vis most other competing filters especially in higher dimensional dynamic system identification problems including cases that may demand estimating relatively minor variations in the parameter values from their reference states. (C) 2014 Elsevier Ltd. All rights reserved.

Unrestricted Skyrme-tensor time-dependent Hartree-Fock model and its application to the nuclear response from spherical to triaxial nuclei

The nuclear time-dependent Hartree-Fock model formulated in three-dimensional space, based on the full standard Skyrme energy density functional complemented with the tensor force, is presented. Full self-consistency is achieved by the model. The application to the isovector giant dipole resonance is discussed in the linear limit, ranging from spherical nuclei (16O and 120Sn) to systems displaying axial or triaxial deformation (24Mg, 28Si, 178Os, 190W and 238U). Particular attention is paid to the spin-dependent terms from the central sector of the functional, recently included together with the tensor. They turn out to be capable of producing a qualitative change on the strength distribution in this channel. The effect on the deformation properties is also discussed. The quantitative effects on the linear response are small and, overall, the giant dipole energy remains unaffected. Calculations are compared to predictions from the (quasi)-particle random-phase approximation and experimental data where available, finding good agreement

Deviation from the sech2 superradiant emission law in a two-level atomic system

The atomic superradiant emission is treated in the single-particle mean-field approximation. A single-particle Hamiltonian, which represents a dressed two-level atom in a radiation field, can be obtained and it is verified that it describes the transient regime of the emission process. While the line-shape emission for a bare atom follows the sech2 law, for the dressed atom the line shape deviates appreciably from this law and it is verified that the deviation depends crucially on the ratio of the dynamic frequency shift to the transition frequency. This kind of deviation is observed in experimental results. © 1990 The American Physical Society.

Adaptive tree multigrids and simplified spherical harmonics approximation in deterministic neutral and charged particle transport

A new deterministic three-dimensional neutral and charged particle transport code, MultiTrans, has been developed. In the novel approach, the adaptive tree multigrid technique is used in conjunction with simplified spherical harmonics approximation of the Boltzmann transport equation. The development of the new radiation transport code started in the framework of the Finnish boron neutron capture therapy (BNCT) project. Since the application of the MultiTrans code to BNCT dose planning problems, the testing and development of the MultiTrans code has continued in conventional radiotherapy and reactor physics applications. In this thesis, an overview of different numerical radiation transport methods is first given. Special features of the simplified spherical harmonics method and the adaptive tree multigrid technique are then reviewed. The usefulness of the new MultiTrans code has been indicated by verifying and validating the code performance for different types of neutral and charged particle transport problems, reported in separate publications.

Uniform stability of a particle approximation of the optimal filter derivative

Sequential Monte Carlo methods, also known as particle methods, are a widely used set of computational tools for inference in non-linear non-Gaussian state-space models. In many applications it may be necessary to compute the sensitivity, or derivative, of the optimal filter with respect to the static parameters of the state-space model; for instance, in order to obtain maximum likelihood model parameters of interest, or to compute the optimal controller in an optimal control problem. In Poyiadjis et al. [2011] an original particle algorithm to compute the filter derivative was proposed and it was shown using numerical examples that the particle estimate was numerically stable in the sense that it did not deteriorate over time. In this paper we substantiate this claim with a detailed theoretical study. Lp bounds and a central limit theorem for this particle approximation of the filter derivative are presented. It is further shown that under mixing conditions these Lp bounds and the asymptotic variance characterized by the central limit theorem are uniformly bounded with respect to the time index. We demon- strate the performance predicted by theory with several numerical examples. We also use the particle approximation of the filter derivative to perform online maximum likelihood parameter estimation for a stochastic volatility model.

ON THE INDEPENDENT-PARTICLE APPROXIMATION OF GAUGE-THEORIES - A SIMPLE EXAMPLE

In this work the independent particle model formulation is studied as a mean-field approximation of gauge theories using the path integral approach in the framework of quantum electrodynamics in 1 + 1 dimensions. It is shown how a mean-field approximation scheme can be applied to fit an effective potential to an independent particle model, building a straightforward relation between the model and the associated gauge field theory. An example is made considering the problem of massive Dirac fermions on a line, the so called massive Schwinger model. An interesting result is found, indicating a behaviour of screening of the charges in the relativistic limit of strong coupling. A forthcoming application of the method developed to confining potentials in independent quark models for QCD is in view and is briefly discussed.

Polynomial approximation using particle swarm optimization of lineal enhanced neural networks with no hidden layers.

This paper presents some ideas about a new neural network architecture that can be compared to a Taylor analysis when dealing with patterns. Such architecture is based on lineal activation functions with an axo-axonic architecture. A biological axo-axonic connection between two neurons is defined as the weight in a connection in given by the output of another third neuron. This idea can be implemented in the so called Enhanced Neural Networks in which two Multilayer Perceptrons are used; the first one will output the weights that the second MLP uses to computed the desired output. This kind of neural network has universal approximation properties even with lineal activation functions. There exists a clear difference between cooperative and competitive strategies. The former ones are based on the swarm colonies, in which all individuals share its knowledge about the goal in order to pass such information to other individuals to get optimum solution. The latter ones are based on genetic models, that is, individuals can die and new individuals are created combining information of alive one; or are based on molecular/celular behaviour passing information from one structure to another. A swarm-based model is applied to obtain the Neural Network, training the net with a Particle Swarm algorithm.

Adiabatic approximation for dynamics of a particle in the field of a tapered solenoid /

"AEC Contract AT(04-3)-400."

A pilot study on the effect of indoor particle sources on indoor particle concentration in residential houses

Characterization of indoor particle sources from 14 residential houses in Brisbane, Australia, was performed. The approximation of PM2.5 and the submicrometre particle number concentrations were measured simultaneously for more than 48 h in the kitchen of all the houses by using a photometer (DustTrak) and a condensation particle counter (CPC), respectively. From the real time indoor particle concentration data and a diary of indoor activities, the indoor particle sources were identified. The study found that among the indoor activities recorded in this study, frying, grilling, stove use, toasting, cooking pizza, smoking, candle vaporizing eucalyptus oil and fan heater use, could elevate the indoor particle number concentration levels by more than five times. The indoor approximation of PM2.5 concentrations could be close to 90 times, 30 times and three times higher than the background levels during grilling, frying and smoking, respectively.

Vector Evaluated Particle Swarm Optimization (VEPSO) of Supersonic Ejector for Hydrogen Fuel Cells

Fuel cells are emerging as alternate green power producers for both large power production and for use in automobiles. Hydrogen is seen as the best option as a fuel; however, hydrogen fuel cells require recirculation of unspent hydrogen. A supersonic ejector is an apt device for recirculation in the operating regimes of a hydrogen fuel cell. Optimal ejectors have to be designed to achieve best performances. The use of the vector evaluated particle swarm optimization technique to optimize supersonic ejectors with a focus on its application for hydrogen recirculation in fuel cells is presented here. Two parameters, compression ratio and efficiency, have been identified as the objective functions to be optimized. Their relation to operating and design parameters of ejector is obtained by control volume based analysis using a constant area mixing approximation. The independent parameters considered are the area ratio and the exit Mach number of the nozzle. The optimization is carried out at a particularentrainment ratio and results in a set of nondominated solutions, the Pareto front. A set of such curves can be used for choosing the optimal design parameters of the ejector.

Smoothed Particle Hydrodynamics (SPH): an Overview and Recent Developments

Smoothed particle hydrodynamics (SPH) is a meshfree particle method based on Lagrangian formulation, and has been widely applied to different areas in engineering and science. This paper presents an overview on the SPH method and its recent developments, including (1) the need for meshfree particle methods, and advantages of SPH, (2) approximation schemes of the conventional SPH method and numerical techniques for deriving SPH formulations for partial differential equations such as the Navier-Stokes (N-S) equations, (3) the role of the smoothing kernel functions and a general approach to construct smoothing kernel functions, (4) kernel and particle consistency for the SPH method, and approaches for restoring particle consistency, (5) several important numerical aspects, and (6) some recent applications of SPH. The paper ends with some concluding remarks.

On the transport properties of fluid-particle flow

The hydrodynamic forces acting on a solid particle in a viscous, incompressible fluid medium at low Reynolds number flow is investigated mathematically as a prerequisite to the understanding of transport processes in two-phase flow involving solid particles and fluid. Viscous interaction between a small number of spherical particles and continuous solid boundaries as well as fluid interface are analyzed under a “point-force” approximation. Non-spherical and elastic spherical particles in a simple shear flow area are then considered. Non-steady motion of a spherical particle is briefly touched upon to illustrate the transient effect of particle motion.

A macroscopic continuum description of particle-fluid flow is formulated in terms of spatial averages yielding a set of particle continuum and bulk fluid equations. Phenomenological formulas describing the transport processes in a fluid medium are extended to cases where the volume concentration of solid particles is sufficiently high to exert an important influence. Hydrodynamic forces acting on a spherical solid particle in such a system, e.g. drag, torque, rotational coupling force, and viscous collision force between streams of different sized particles moving relative to each other are obtained. Phenomenological constants, such as the shear viscosity coefficient, and the diffusion coefficient of the bulk fluid, are found as a function of the material properties of the constituents of the two-phase system and the volume concentration of solid. For transient heat conduction phenomena, it is found that the introduction of a complex conductivity for the bulk fluid permits a simple mathematical description of this otherwise complicated process. The rate of heat transfer between particle continuum and bulk fluid is also investigated by means of an Oseen-type approximation to the energy equation.