970 resultados para CATALYZED COUPLING REACTIONS
Resumo:
We present reaction free energy calculations using the adaptive buffered force mixing quantum mechanics/molecular mechanics (bf-QM/MM) method. The bf-QM/MM method combines nonadaptive electrostatic embedding QM/MM calculations with extended and reduced QM regions to calculate accurate forces on all atoms, which can be used in free energy calculation methods that require only the forces and not the energy. We calculate the free energy profiles of two reactions in aqueous solution: the nucleophilic substitution reaction of methyl chloride with a chloride anion and the deprotonation reaction of the tyrosine side chain. We validate the bf-QM/MM method against a full QM simulation, and show that it correctly reproduces both geometrical properties and free energy profiles of the QM model, while the electrostatic embedding QM/MM method using a static QM region comprising only the solute is unable to do so. The bf-QM/MM method is not explicitly dependent on the details of the QM and MM methods, so long as it is possible to compute QM forces in a small region and MM forces in the rest of the system, as in a conventional QM/MM calculation. It is simple, with only a few parameters needed to control the QM calculation sizes, and allows (but does not require) a varying and adapting QM region which is necessary for simulating solutions.
Resumo:
This paper presents stochastic implicit coupling method intended for use in Monte-Carlo (MC) based reactor analysis systems that include burnup and thermal hydraulic (TH) feedbacks. Both feedbacks are essential for accurate modeling of advanced reactor designs and analyses of associated fuel cycles. In particular, we investigate the effect of different burnup-TH coupling schemes on the numerical stability and accuracy of coupled MC calculations. First, we present the beginning of time step method which is the most commonly used. The accuracy of this method depends on the time step length and it is only conditionally stable. This work demonstrates that even for relatively short time steps, this method can be numerically unstable. Namely, the spatial distribution of neutronic and thermal hydraulic parameters, such as nuclide densities and temperatures, exhibit oscillatory behavior. To address the numerical stability issue, new implicit stochastic methods are proposed. The methods solve the depletion and TH problems simultaneously and use under-relaxation to speed up convergence. These methods are numerically stable and accurate even for relatively large time steps and require less computation time than the existing methods. © 2013 Elsevier Ltd. All rights reserved.
Resumo:
Coupled hydrology and water quality models are an important tool today, used in the understanding and management of surface water and watershed areas. Such problems are generally subject to substantial uncertainty in parameters, process understanding, and data. Component models, drawing on different data, concepts, and structures, are affected differently by each of these uncertain elements. This paper proposes a framework wherein the response of component models to their respective uncertain elements can be quantified and assessed, using a hydrological model and water quality model as two exemplars. The resulting assessments can be used to identify model coupling strategies that permit more appropriate use and calibration of individual models, and a better overall coupled model response. One key finding was that an approximate balance of water quality and hydrological model responses can be obtained using both the QUAL2E and Mike11 water quality models. The balance point, however, does not support a particularly narrow surface response (or stringent calibration criteria) with respect to the water quality calibration data, at least in the case examined here. Additionally, it is clear from the results presented that the structural source of uncertainty is at least as significant as parameter-based uncertainties in areal models. © 2012 John Wiley & Sons, Ltd.
Resumo:
Cell biology is characterised by low molecule numbers and coupled stochastic chemical reactions with intrinsic noise permeating and dominating the interactions between molecules. Recent work [9] has shown that in such environments there are hard limits on the accuracy with which molecular populations can be controlled and estimated. These limits are predicated on a continuous diffusion approximation of the target molecule (although the remainder of the system is non-linear and discrete). The principal result of [9] assumes that the birth rate of the signalling species is linearly dependent on the target molecule population size. In this paper, we investigate the situation when the entire system is kept discrete, and arbitrary non-linear coupling is allowed between the target molecule and downstream signalling molecules. In this case it is possible, by relying solely on the event triggered nature of control and signalling reactions, to define non-linear reaction rate modulation schemes that achieve improved performance in certain parameter regimes. These schemes would not appear to be biologically relevant, raising the question of what are an appropriate set of assumptions for obtaining biologically meaningful results. © 2013 EUCA.
Resumo:
Due to technological limitations, robot actuators are often designed for specific tasks with narrow performance goals, whereas a wide range of behaviors is necessary for autonomous robots in uncertain complex environments. In an effort to increase the versatility of actuators, we introduce a new concept of multimodal actuation (MMA) that employs dynamic coupling in the form of clutches and brakes to change its mode of operation. The dynamic coupling allows motors and passive elements such as springs to be engaged and disengaged within a single actuator. We apply the concept to a linear series elastic actuator which uses friction brakes controlled online for the dynamic coupling. With this prototype, we are able to demonstrate several modes of operation including stiff position control, series elastic actuation as well as the possibility to store and release energy in a controlled manner for explosive tasks such as jumping. In this paper, we model the proposed concept of actuation and show a systematic performance analysis of the physical prototype that we developed in our laboratory. © 1996-2012 IEEE.
Resumo:
Due to technological limitations robot actuators are often designed for specific tasks with narrow performance goals, whereas a wide range of output and behaviours is necessary for robots to operate autonomously in uncertain complex environments. We present a design framework that employs dynamic couplings in the form of brakes and clutches to increase the performance and diversity of linear actuators. The couplings are used to switch between a diverse range of discrete modes of operation within a single actuator. We also provide a design solution for miniaturized couplings that use dry friction to produce rapid switching and high braking forces. The couplings are designed so that once engaged or disengaged no extra energy is consumed. We apply the design framework and coupling design to a linear series elastic actuator (SEA) and show that this relatively simple implementation increases the performance and adds new behaviours to the standard design. Through a number of performance tests we are able to show rapid switching between a high and a low impedance output mode; that the actuator's spring can be charged to produce short bursts of high output power; and that the actuator has additional passive and rigid modes that consume no power once activated. Robots using actuators from this design framework would see a vast increase in their behavioural diversity and improvements in their performance not yet possible with conventional actuator design. © 2012 IEEE.
Resumo:
We investigate numerically the self-imaging effect in a system of multiple coupled photonic crystal waveguides (M-CPCWs) with asymmetric coupling. Then two couplers of 2-CPCWs and 3-CPCWs are cascaded to form an ultracompact triplexer by employing coupling and decoupling of M-CPCWs. The wavelength of 1310 nm propagates along the input direction because the M-CPCWs are decoupled at the same decoupling frequency. The other two wavelengths (1490 and 1550 nm) are separated by combining multimode interference and the dual mode coupling effect. Only by introducing a single defect near the crossing point between two output photonic crystal waveguides (PCWs) are the high extinction ratios for the three wavelengths achieved simultaneously.
Resumo:
The photoluminescence (PL) intensity enhancement and suppression mechanism on surface plasmons (SPs) coupling with InGaN/GaN quantum wells (QWs) have been systematically studied. The SP-QW coupling behaviors in the areas of GaN cap layer coated with silver thin film were compared at different temperatures and excitation powers. It is found that the internal quantum efficiency (IQE) of the light emitting diodes (LEDs) varies with temperature and excitation power, which in turn results in anomalous emission enhancement and suppression tendency related to SP-QW coupling. The observation is explained by the balance between the extraction efficiency of SPs and the IQE of LEDs
Resumo:
The characteristics of whispering-gallery modes (WGMs) in 3-D cylindrical, square, and triangular microcavities with vertical optical confinement of semiconductors are numerically investigated by the finite-difference time-domain (FDTD) technique. For a microcylinder with a vertical refractive index 3.17/3.4/3.17 and a center layer thickness 0.2 mu m, Q-factors of transverse electric (TE) WGMs around wavelength 1550 nm are smaller than 10(3), as the radius R < 4 mu m and reach the orders of 10(4) and 10(6) as R = 5 and 6 mu m, respectively. However, the Q-factor of transverse magnetic (TM) WGMs at wavelength 1.659 mu m reaches 7.5 x 10(5) as R = 1 mu m. The mode coupling between the WGMs and vertical radiation modes in the cladding layer results in vertical radiation loss for the WGMs. In the microcylinder, the mode wavelength of TM WGM is larger than the cutoff wavelength of the vertical radiation mode with the same mode numbers, so TM WGMs cannot couple with the vertical radiation mode and have high Q-factor. In contrast, TE WGMs can couple with the corresponding vertical radiation mode in the 3-D microcylinder as R < 5 mu m. However, the mode wavelength of the TE WGM approaches (is larger than) the cutoff wavelength of the corresponding radiation modes at R = 5 mu m (6 mu m), so TE WGMs have high Q-factors in such microcylinders too. The results show that a critical lateral size is required for obtaining high, Q-factor TE WGMs in the 3-D microcylinder. For 3-D square and triangular microcavities, we also find that the Q-factor of TM WGM is larger than that of TE WGM.