Perspective on Diabatic Models of Chemical Reactivity as Illustrated by the Gas-Phase SN2 Reaction of Acetate Ion with 1,2-Dichloroethane

PubMed Central

Valero, Rosendo; Song, Lingchun; Gao, Jiali; Truhlar, Donald G.

2009-01-01

Diabatic models are widely employed for studying chemical reactivity in condensed phases and enzymes, but there has been little discussion of the pros and cons of various diabatic representations for this purpose. Here we discuss and contrast six different schemes for computing diabatic potentials for a charge rearrangement reaction. They include (i) the variational diabatic configurations (VDC) constructed by variationally optimizing individual valence bond structures and (ii) the consistent diabatic configurations (CDC) obtained by variationally optimizing the ground-state adiabatic energy, both in the nonorthogonal molecular orbital valence bond (MOVB) method, along with the orthogonalized (iii) VDC-MOVB and (iv) CDC-MOVB models. In addition, we consider (v) the fourfold way (based on diabatic molecular orbitals and configuration uniformity), and (vi) empirical valence bond (EVB) theory. To make the considerations concrete, we calculate diabatic electronic states and diabatic potential energies along the reaction path that connects the reactant and the product ion-molecule complexes of the gas-phase bimolecular nucleophilic substitution (SN2) reaction of 1,2-dichloethane (DCE) with acetate ion, which is a model reaction corresponding to the reaction catalyzed by haloalkane dehalogenase. We utilize ab initio block-localized molecular orbital theory to construct the MOVB diabatic states and ab initio multi-configuration quasidegenerate perturbation theory to construct the fourfold-way diabatic states; the latter are calculated at reaction path geometries obtained with the M06-2X density functional. The EVB diabatic states are computed with parameters taken from the literature. The MOVB and fourfold-way adiabatic and diabatic potential energy profiles along the reaction path are in qualitative but not quantitative agreement with each other. In order to validate that these wave-function-based diabatic states are qualitatively correct, we show that the reaction energy and barrier for the adiabatic ground state, obtained with these methods, agree reasonably well with the results of high-level calculations using the composite G3SX and G3SX(MP3) methods and the BMC-CCSD multi-coefficient correlation method. However, a comparison of the EVB gas-phase adiabatic ground-state reaction path with those obtained from MOVB and with the fourfold way reveals that the EVB reaction path geometries show a systematic shift towards the products region, and that the EVB lowest-energy path has a much lower barrier. The free energies of solvation and activation energy in water reported from dynamical calculations based on EVB also imply a low activation barrier in the gas phase. In addition, calculations of the free energy of solvation using the recently proposed SM8 continuum solvation model with CM4M partial atomic charges lead to an activation barrier in reasonable agreement with experiment only when the geometries and the gas-phase barrier are those obtained from electronic structure calculations, i.e., methods i–v. These comparisons show the danger of basing the diabatic states on molecular mechanics without the explicit calculation of electronic wave functions. Furthermore, comparison of schemes i–v with one another shows that significantly different quantitative results can be obtained by using different methods for extracting diabatic states from wave function calculations, and it is important for each user to justify the choice of diabatization method in the context of its intended use. PMID:20047005

Rock climbing: A local-global algorithm to compute minimum energy and minimum free energy pathways.

PubMed

Templeton, Clark; Chen, Szu-Hua; Fathizadeh, Arman; Elber, Ron

2017-10-21

The calculation of minimum energy or minimum free energy paths is an important step in the quantitative and qualitative studies of chemical and physical processes. The computations of these coordinates present a significant challenge and have attracted considerable theoretical and computational interest. Here we present a new local-global approach to study reaction coordinates, based on a gradual optimization of an action. Like other global algorithms, it provides a path between known reactants and products, but it uses a local algorithm to extend the current path in small steps. The local-global approach does not require an initial guess to the path, a major challenge for global pathway finders. Finally, it provides an exact answer (the steepest descent path) at the end of the calculations. Numerical examples are provided for the Mueller potential and for a conformational transition in a solvated ring system.

The approach for shortest paths in fire succor based on component GIS technology

NASA Astrophysics Data System (ADS)

Han, Jie; Zhao, Yong; Dai, K. W.

2007-06-01

Fire safety is an important issue for the national economy and people's living. Efficiency and exactness of fire department succor directly relate to safety of peoples' lives and property. Many disadvantages of the traditional fire system have been emerged in practical applications. The preparation of pumpers is guided by wireless communication or wire communication, so its real-time and accurate performances are much poorer. The information about the reported fire, such as the position, disaster and map, et al., for alarm and command was processed by persons, which slows the reaction speed and delays the combat opportunity. In order to solve these disadvantages, it has an important role to construct a modern fire command center based on high technology. The construction of modern fire command center can realize the modernization and automation of fire command and management. It will play a great role in protecting safety of peoples' lives and property. The center can enhance battle ability and can reduce the direct and indirect loss of fire damage at most. With the development of science technology, Geographic Information System (GIS) has becoming a new information industry for hardware production, software development, data collection, space analysis and counseling. With the popularization of computers and the development of GIS, GIS has gained increasing broad applications for its strong functionality. Network analysis is one of the most important functions of GIS, and the most elementary and pivotal issue of network analysis is the calculation of shortest paths. The shortest paths are mostly applied to some emergent systems such as 119 fire alarms. These systems mainly require that the computation time of the optimal path should be 1-3 seconds. And during traveling, the next running path of the vehicles should be calculated in time. So the implement of the shortest paths must have a high efficiency. In this paper, the component GIS technology was applied to collect and record the data information (such as, the situation of this disaster, map and road status et al) of the reported fire firstly. The ant colony optimization was used to calculate the shortest path of fire succor secondly. The optimization results were sent to the pumpers, which can let pumpers choose the shortest paths intelligently and come to fire position with least time. The programming method for shortest paths is proposed in section 3. There are three parts in this section. The elementary framework of the proposed programming method is presented in part one. The systematic framework of GIS component is described in part two. The ant colony optimization employed is presented in part three. In section 4, a simple application instance was presented to demonstrate the proposed programming method. There are three parts in this section. The distributed Web application based on component GIS was described in part one. The optimization results without traffic constraint were presented in part two. The optimization results with traffic constraint were presented in part three. The contributions of this paper can be summarized as follows. (1) It proposed an effective approach for shortest paths in fire succor based on component GIS technology. This proposed approach can achieve the real-time decisions of shortest paths for fire succor. (2) It applied the ant colony optimization to implement the shortest path decision. The traffic information was considered in the shortest path decision using ant colony optimization. The final application instance suggests that the proposed approach is feasible, correct and valid.

Cumulative Significance of Hyporheic Exchange and Biogeochemical Processing in River Networks

NASA Astrophysics Data System (ADS)

Harvey, J. W.; Gomez-Velez, J. D.

2014-12-01

Biogeochemical reactions in rivers that decrease excessive loads of nutrients, metals, organic compounds, etc. are enhanced by hydrologic interactions with microbially and geochemically active sediments of the hyporheic zone. The significance of reactions in individual hyporheic flow paths has been shown to be controlled by the contact time between river water and sediment and the intrinsic reaction rate in the sediment. However, little is known about how the cumulative effects of hyporheic processing in large river basins. We used the river network model NEXSS (Gomez-Velez and Harvey, submitted) to simulate hyporheic exchange through synthetic river networks based on the best available models of network topology, hydraulic geometry and scaling of geomorphic features, grain size, hydraulic conductivity, and intrinsic reaction rates of nutrients and metals in river sediment. The dimensionless reaction significance factor, RSF (Harvey et al., 2013) was used to quantify the cumulative removal fraction of a reactive solute by hyporheic processing. SF scales reaction progress in a single pass through the hyporheic zone with the proportion of stream discharge passing through the hyporheic zone for a specified distance. Reaction progress is optimal where the intrinsic reaction timescale in sediment matches the residence time of hyporheic flow and is less efficient in longer residence time hyporheic flow as a result of the decreasing proportion of river flow that is processed by longer residence time hyporheic flow paths. In contrast, higher fluxes through short residence time hyporheic flow paths may be inefficient because of the repeated surface-subsurface exchanges required to complete the reaction. Using NEXSS we found that reaction efficiency may be high in both small streams and large rivers, although for different reasons. In small streams reaction progress generally is dominated by faster pathways of vertical exchange beneath submerged bedforms. Slower exchange beneath meandering river banks mainly has importance only in large rivers. For solutes entering networks in proportion to water inputs it is the lower order streams that tend to dominate cumulative reaction progress.

Comparison of classical reaction paths and tunneling paths studied with the semiclassical instanton theory.

PubMed

Meisner, Jan; Markmeyer, Max N; Bohner, Matthias U; Kästner, Johannes

2017-08-30

Atom tunneling in the hydrogen atom transfer reaction of the 2,4,6-tri-tert-butylphenyl radical to 3,5-di-tert-butylneophyl, which has a short but strongly curved reaction path, was investigated using instanton theory. We found the tunneling path to deviate qualitatively from the classical intrinsic reaction coordinate, the steepest-descent path in mass-weighted Cartesian coordinates. To perform that comparison, we implemented a new variant of the predictor-corrector algorithm for the calculation of the intrinsic reaction coordinate. We used the reaction force analysis method as a means to decompose the reaction barrier into structural and electronic components. Due to the narrow energy barrier, atom tunneling is important in the abovementioned reaction, even above room temperature. Our calculated rate constants between 350 K and 100 K agree well with experimental values. We found a H/D kinetic isotope effect of almost 10 6 at 100 K. Tunneling dominates the protium transfer below 400 K and the deuterium transfer below 300 K. We compared the lengths of the tunneling path and the classical path for the hydrogen atom transfer in the reaction HCl + Cl and quantified the corner cutting in this reaction. At low temperature, the tunneling path is about 40% shorter than the classical path.

Time optimal paths for high speed maneuvering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reister, D.B.; Lenhart, S.M.

1993-01-01

Recent theoretical results have completely solved the problem of determining the minimum length path for a vehicle with a minimum turning radius moving from an initial configuration to a final configuration. Time optimal paths for a constant speed vehicle are a subset of the minimum length paths. This paper uses the Pontryagin maximum principle to find time optimal paths for a constant speed vehicle. The time optimal paths consist of sequences of axes of circles and straight lines. The maximum principle introduces concepts (dual variables, bang-bang solutions, singular solutions, and transversality conditions) that provide important insight into the nature ofmore » the time optimal paths. We explore the properties of the optimal paths and present some experimental results for a mobile robot following an optimal path.« less

Incorporating Linear Synchronous Transit Interpolation into the Growing String Method: Algorithm and Applications.

PubMed

Behn, Andrew; Zimmerman, Paul M; Bell, Alexis T; Head-Gordon, Martin

2011-12-13

The growing string method is a powerful tool in the systematic study of chemical reactions with theoretical methods which allows for the rapid identification of transition states connecting known reactant and product structures. However, the efficiency of this method is heavily influenced by the choice of interpolation scheme when adding new nodes to the string during optimization. In particular, the use of Cartesian coordinates with cubic spline interpolation often produces guess structures which are far from the final reaction path and require many optimization steps (and thus many energy and gradient calculations) to yield a reasonable final structure. In this paper, we present a new method for interpolating and reparameterizing nodes within the growing string method using the linear synchronous transit method of Halgren and Lipscomb. When applied to the alanine dipeptide rearrangement and a simplified cationic alkyl ring condensation reaction, a significant speedup in terms of computational cost is achieved (30-50%).

Optimal Path Determination for Flying Vehicle to Search an Object

NASA Astrophysics Data System (ADS)

Heru Tjahjana, R.; Heri Soelistyo U, R.; Ratnasari, L.; Irawanto, B.

2018-01-01

In this paper, a method to determine optimal path for flying vehicle to search an object is proposed. Background of the paper is controlling air vehicle to search an object. Optimal path determination is one of the most popular problem in optimization. This paper describe model of control design for a flying vehicle to search an object, and focus on the optimal path that used to search an object. In this paper, optimal control model is used to control flying vehicle to make the vehicle move in optimal path. If the vehicle move in optimal path, then the path to reach the searched object also optimal. The cost Functional is one of the most important things in optimal control design, in this paper the cost functional make the air vehicle can move as soon as possible to reach the object. The axis reference of flying vehicle uses N-E-D (North-East-Down) coordinate system. The result of this paper are the theorems which say that the cost functional make the control optimal and make the vehicle move in optimal path are proved analytically. The other result of this paper also shows the cost functional which used is convex. The convexity of the cost functional is use for guarantee the existence of optimal control. This paper also expose some simulations to show an optimal path for flying vehicle to search an object. The optimization method which used to find the optimal control and optimal path vehicle in this paper is Pontryagin Minimum Principle.

Effects of reaction-kinetic parameters on modeling reaction pathways in GaN MOVPE growth

NASA Astrophysics Data System (ADS)

Zhang, Hong; Zuo, Ran; Zhang, Guoyi

2017-11-01

In the modeling of the reaction-transport process in GaN MOVPE growth, the selections of kinetic parameters (activation energy Ea and pre-exponential factor A) for gas reactions are quite uncertain, which cause uncertainties in both gas reaction path and growth rate. In this study, numerical modeling of the reaction-transport process for GaN MOVPE growth in a vertical rotating disk reactor is conducted with varying kinetic parameters for main reaction paths. By comparisons of the molar concentrations of major Ga-containing species and the growth rates, the effects of kinetic parameters on gas reaction paths are determined. The results show that, depending on the values of the kinetic parameters, the gas reaction path may be dominated either by adduct/amide formation path, or by TMG pyrolysis path, or by both. Although the reaction path varies with different kinetic parameters, the predicted growth rates change only slightly because the total transport rate of Ga-containing species to the substrate changes slightly with reaction paths. This explains why previous authors using different chemical models predicted growth rates close to the experiment values. By varying the pre-exponential factor for the amide trimerization, it is found that the more trimers are formed, the lower the growth rates are than the experimental value, which indicates that trimers are poor growth precursors, because of thermal diffusion effect caused by high temperature gradient. The effective order for the contribution of major species to growth rate is found as: pyrolysis species > amides > trimers. The study also shows that radical reactions have little effect on gas reaction path because of the generation and depletion of H radicals in the chain reactions when NH2 is considered as the end species.

Computational study on the aminolysis of beta-hydroxy-alpha,beta-unsaturated ester via the favorable path including the formation of alpha-oxo ketene intermediate.

PubMed

Jin, Lu; Xue, Ying; Zhang, Hui; Kim, Chan Kyung; Xie, Dai Qian; Yan, Guo Sen

2008-05-15

The possible mechanisms of the aminolysis of N-methyl-3-(methoxycarbonyl)-4-hydroxy-2-pyridone (beta-hydroxy-alpha,beta-unsaturated ester) with dimethylamine are investigated at the hybrid density functional theory B3LYP/6-31G(d,p) level in the gas phase. Single-point computations at the B3LYP/6-311++G(d,p) and the Becke88-Becke95 1-parameter model BB1K/6-311++G(d,p) levels are performed for more precise energy predictions. Solvent effects are also assessed by single-point calculations at the integral equation formalism polarized continuum model IEFPCM-B3LYP/6-311++G(d,p) and IEFPCM-BB1K/6-311++G(d,p) levels on the gas-phase optimized geometries. Three possible pathways, the concerted pathway (path A), the stepwise pathway involving tetrahedral intermediates (path B), and the stepwise pathway via alpha-oxo ketene intermediate due to the participation of beta-hydroxy (path C), are taken into account for the title reaction. Moreover, path C includes two sequential processes. The first process is to generate alpha-oxo ketene intermediate via the decomposition of N-methyl-3-(methoxycarbonyl)-4-hydroxy-2-pyridone; the second process is the addition of dimethylamine to alpha-oxo ketene intermediate. Our results indicate that path C is more favorable than paths A and B both in the gas phase and in solvent (heptane). In path C, the first process is the rate-determining step, and the second process is revealed to be a [4+2] pseudopericyclic reaction without the energy barrier. Being independent of the concentration of amine, the first process obeys the first-order rate law.

Improving Upon String Methods for Transition State Discovery.

PubMed

Chaffey-Millar, Hugh; Nikodem, Astrid; Matveev, Alexei V; Krüger, Sven; Rösch, Notker

2012-02-14

Transition state discovery via application of string methods has been researched on two fronts. The first front involves development of a new string method, named the Searching String method, while the second one aims at estimating transition states from a discretized reaction path. The Searching String method has been benchmarked against a number of previously existing string methods and the Nudged Elastic Band method. The developed methods have led to a reduction in the number of gradient calls required to optimize a transition state, as compared to existing methods. The Searching String method reported here places new beads on a reaction pathway at the midpoint between existing beads, such that the resolution of the path discretization in the region containing the transition state grows exponentially with the number of beads. This approach leads to favorable convergence behavior and generates more accurate estimates of transition states from which convergence to the final transition states occurs more readily. Several techniques for generating improved estimates of transition states from a converged string or nudged elastic band have been developed and benchmarked on 13 chemical test cases. Optimization approaches for string methods, and pitfalls therein, are discussed.

String method for calculation of minimum free-energy paths in Cartesian space in freely-tumbling systems.

PubMed

Branduardi, Davide; Faraldo-Gómez, José D

2013-09-10

The string method is a molecular-simulation technique that aims to calculate the minimum free-energy path of a chemical reaction or conformational transition, in the space of a pre-defined set of reaction coordinates that is typically highly dimensional. Any descriptor may be used as a reaction coordinate, but arguably the Cartesian coordinates of the atoms involved are the most unprejudiced and intuitive choice. Cartesian coordinates, however, present a non-trivial problem, in that they are not invariant to rigid-body molecular rotations and translations, which ideally ought to be unrestricted in the simulations. To overcome this difficulty, we reformulate the framework of the string method to integrate an on-the-fly structural-alignment algorithm. This approach, referred to as SOMA (String method with Optimal Molecular Alignment), enables the use of Cartesian reaction coordinates in freely tumbling molecular systems. In addition, this scheme permits the dissection of the free-energy change along the most probable path into individual atomic contributions, thus revealing the dominant mechanism of the simulated process. This detailed analysis also provides a physically-meaningful criterion to coarse-grain the representation of the path. To demonstrate the accuracy of the method we analyze the isomerization of the alanine dipeptide in vacuum and the chair-to-inverted-chair transition of β -D mannose in explicit water. Notwithstanding the simplicity of these systems, the SOMA approach reveals novel insights into the atomic mechanism of these isomerizations. In both cases, we find that the dynamics and the energetics of these processes are controlled by interactions involving only a handful of atoms in each molecule. Consistent with this result, we show that a coarse-grained SOMA calculation defined in terms of these subsets of atoms yields nearidentical minimum free-energy paths and committor distributions to those obtained via a highly-dimensional string.

String method for calculation of minimum free-energy paths in Cartesian space in freely-tumbling systems

PubMed Central

Branduardi, Davide; Faraldo-Gómez, José D.

2014-01-01

The string method is a molecular-simulation technique that aims to calculate the minimum free-energy path of a chemical reaction or conformational transition, in the space of a pre-defined set of reaction coordinates that is typically highly dimensional. Any descriptor may be used as a reaction coordinate, but arguably the Cartesian coordinates of the atoms involved are the most unprejudiced and intuitive choice. Cartesian coordinates, however, present a non-trivial problem, in that they are not invariant to rigid-body molecular rotations and translations, which ideally ought to be unrestricted in the simulations. To overcome this difficulty, we reformulate the framework of the string method to integrate an on-the-fly structural-alignment algorithm. This approach, referred to as SOMA (String method with Optimal Molecular Alignment), enables the use of Cartesian reaction coordinates in freely tumbling molecular systems. In addition, this scheme permits the dissection of the free-energy change along the most probable path into individual atomic contributions, thus revealing the dominant mechanism of the simulated process. This detailed analysis also provides a physically-meaningful criterion to coarse-grain the representation of the path. To demonstrate the accuracy of the method we analyze the isomerization of the alanine dipeptide in vacuum and the chair-to-inverted-chair transition of β-D mannose in explicit water. Notwithstanding the simplicity of these systems, the SOMA approach reveals novel insights into the atomic mechanism of these isomerizations. In both cases, we find that the dynamics and the energetics of these processes are controlled by interactions involving only a handful of atoms in each molecule. Consistent with this result, we show that a coarse-grained SOMA calculation defined in terms of these subsets of atoms yields nearidentical minimum free-energy paths and committor distributions to those obtained via a highly-dimensional string. PMID:24729762

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reister, D.B.; Lenhart, S.M.

Recent theoretical results have completely solved the problem of determining the minimum length path for a vehicle with a minimum turning radius moving from an initial configuration to a final configuration. Time optimal paths for a constant speed vehicle are a subset of the minimum length paths. This paper uses the Pontryagin maximum principle to find time optimal paths for a constant speed vehicle. The time optimal paths consist of sequences of axes of circles and straight lines. The maximum principle introduces concepts (dual variables, bang-bang solutions, singular solutions, and transversality conditions) that provide important insight into the nature ofmore » the time optimal paths. We explore the properties of the optimal paths and present some experimental results for a mobile robot following an optimal path.« less

Developing Chemistry and Kinetic Modeling Tools for Low-Temperature Plasma Simulations

NASA Astrophysics Data System (ADS)

Jenkins, Thomas; Beckwith, Kris; Davidson, Bradley; Kruger, Scott; Pankin, Alexei; Roark, Christine; Stoltz, Peter

2015-09-01

We discuss the use of proper orthogonal decomposition (POD) methods in VSim, a FDTD plasma simulation code capable of both PIC/MCC and fluid modeling. POD methods efficiently generate smooth representations of noisy self-consistent or test-particle PIC data, and are thus advantageous in computing macroscopic fluid quantities from large PIC datasets (e.g. for particle-based closure computations) and in constructing optimal visual representations of the underlying physics. They may also confer performance advantages for massively parallel simulations, due to the significant reduction in dataset sizes conferred by truncated singular-value decompositions of the PIC data. We also demonstrate how complex LTP chemistry scenarios can be modeled in VSim via an interface with MUNCHKIN, a developing standalone python/C++/SQL code that identifies reaction paths for given input species, solves 1D rate equations for the time-dependent chemical evolution of the system, and generates corresponding VSim input blocks with appropriate cross-sections/reaction rates. MUNCHKIN also computes reaction rates from user-specified distribution functions, and conducts principal path analyses to reduce the number of simulated chemical reactions. Supported by U.S. Department of Energy SBIR program, Award DE-SC0009501.

Exploring mechanisms of a tropospheric archetype: CH{sub 3}O{sub 2} + NO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Launder, Andrew M.; Agarwal, Jay; Schaefer, Henry F., E-mail: ccq@uga.edu

Methylperoxy radical (CH{sub 3}O{sub 2}) and nitric oxide (NO) contribute to the propagation of photochemical smog in the troposphere via the production of methoxy radical (CH{sub 3}O) and nitrogen dioxide (NO{sub 2}). This reaction system also furnishes trace quantities of methyl nitrate (CH{sub 3}ONO{sub 2}), a sink for reactive NO{sub x} species. Here, the CH{sub 3}O{sub 2} + NO reaction is examined with highly reliable coupled-cluster methods. Specifically, equilibrium geometries for the reactants, products, intermediates, and transition states of the ground-state potential energy surface are characterized. Relative reaction enthalpies at 0 K (ΔH{sub 0K}) are reported; these values are comprisedmore » of electronic energies extrapolated to the complete basis set limit of CCSDT(Q) and zero-point vibrational energies computed at CCSD(T)/cc-pVTZ. A two-part mechanism involving CH{sub 3}O and NO{sub 2} production followed by radical recombination to CH{sub 3}ONO{sub 2} is determined to be the primary channel for formation of CH{sub 3}ONO{sub 2} under tropospheric conditions. Constrained optimizations of the reaction paths at CCSD(T)/cc-pVTZ suggest that the homolytic bond dissociations involved in this reaction path are barrierless.« less

Amoeba-Inspired Heuristic Search Dynamics for Exploring Chemical Reaction Paths.

PubMed

Aono, Masashi; Wakabayashi, Masamitsu

2015-09-01

We propose a nature-inspired model for simulating chemical reactions in a computationally resource-saving manner. The model was developed by extending our previously proposed heuristic search algorithm, called "AmoebaSAT [Aono et al. 2013]," which was inspired by the spatiotemporal dynamics of a single-celled amoeboid organism that exhibits sophisticated computing capabilities in adapting to its environment efficiently [Zhu et al. 2013]. AmoebaSAT is used for solving an NP-complete combinatorial optimization problem [Garey and Johnson 1979], "the satisfiability problem," and finds a constraint-satisfying solution at a speed that is dramatically faster than one of the conventionally known fastest stochastic local search methods [Iwama and Tamaki 2004] for a class of randomly generated problem instances [ http://www.cs.ubc.ca/~hoos/5/benchm.html ]. In cases where the problem has more than one solution, AmoebaSAT exhibits dynamic transition behavior among a variety of the solutions. Inheriting these features of AmoebaSAT, we formulate "AmoebaChem," which explores a variety of metastable molecules in which several constraints determined by input atoms are satisfied and generates dynamic transition processes among the metastable molecules. AmoebaChem and its developed forms will be applied to the study of the origins of life, to discover reaction paths for which expected or unexpected organic compounds may be formed via unknown unstable intermediates and to estimate the likelihood of each of the discovered paths.

Unusual reaction paths of SN2 nucleophile substitution reactions CH4 + H- → CH4 + H- and CH4 + F- → CH3F + H-: Quantum chemical calculations

NASA Astrophysics Data System (ADS)

Minyaev, Ruslan M.; Quapp, Wolfgang; Schmidt, Benjamin; Getmanskii, Ilya V.; Koval, Vitaliy V.

2013-11-01

Quantum chemical (CCSD(full)/6-311++G(3df,3pd), CCSD(T)(full)/6-311++G(3df,3pd)) and density function theory (B3LYP/6-311++G(3df,3pd)) calculations were performed for the SN2 nucleophile substitution reactions CH4 + H- → CH4 + H- and CH4 + F- → CH3F + H-. The calculated gradient reaction pathways for both reactions have an unusual behavior. An unusual stationary point of index 2 lies on the gradient reaction path. Using Newton trajectories for the reaction path, we can detect VRI point at which the reaction path branches.

Energy-optimal path planning by stochastic dynamically orthogonal level-set optimization

NASA Astrophysics Data System (ADS)

Subramani, Deepak N.; Lermusiaux, Pierre F. J.

2016-04-01

A stochastic optimization methodology is formulated for computing energy-optimal paths from among time-optimal paths of autonomous vehicles navigating in a dynamic flow field. Based on partial differential equations, the methodology rigorously leverages the level-set equation that governs time-optimal reachability fronts for a given relative vehicle-speed function. To set up the energy optimization, the relative vehicle-speed and headings are considered to be stochastic and new stochastic Dynamically Orthogonal (DO) level-set equations are derived. Their solution provides the distribution of time-optimal reachability fronts and corresponding distribution of time-optimal paths. An optimization is then performed on the vehicle's energy-time joint distribution to select the energy-optimal paths for each arrival time, among all stochastic time-optimal paths for that arrival time. Numerical schemes to solve the reduced stochastic DO level-set equations are obtained, and accuracy and efficiency considerations are discussed. These reduced equations are first shown to be efficient at solving the governing stochastic level-sets, in part by comparisons with direct Monte Carlo simulations. To validate the methodology and illustrate its accuracy, comparisons with semi-analytical energy-optimal path solutions are then completed. In particular, we consider the energy-optimal crossing of a canonical steady front and set up its semi-analytical solution using a energy-time nested nonlinear double-optimization scheme. We then showcase the inner workings and nuances of the energy-optimal path planning, considering different mission scenarios. Finally, we study and discuss results of energy-optimal missions in a wind-driven barotropic quasi-geostrophic double-gyre ocean circulation.

A dianionic phosphorane intermediate and transition states in an associative A(N)+D(N) mechanism for the ribonucleaseA hydrolysis reaction.

PubMed

Elsässer, Brigitta; Valiev, Marat; Weare, John H

2009-03-25

The RNaseA enzyme efficiently cleaves phosphodiester bonds in the RNA backbone. Phosphoryl transfer plays a central role in many biochemical reactions, and this is one of the most studied enzymes. However, there remains considerable controversy about the reaction mechanism. Most of this debate centers around the roles of the conserved residues, structures of the transition state or states, the possibility of a stable intermediate, and the charge and structure of this intermediate. In this communication we report calculations of the mechanism of the hydrolysis step in this reaction using a comprehensive QM/MM theoretical approach that includes a high level calculation of the interactions in the QM region, free energy estimates along an NEB optimized reaction path, and the inclusion of the interaction of the protein surroundings and solvent. Contrary to prior calculations we find a stable pentacoordinated dianionic phosphorane intermediate in the reaction path supporting an A(N)+D(N) reaction mechanism. In the transition state in the path from the reactant to the intermediate state (with barrier of 3.96 kcal/mol and intermediate stability of 2.21 kcal/mol) a proton from the attacking water is partially transferred to the His119 residue and the PO bond only partially formed from the remaining nucleophilic OH(-) species (bond order (BO) 0.11). In passing from the intermediate to the product state (barrier 13.22 kcal/mol) the PO bond on the cyclic phosphorane intermediate is nearly broken (BO 0.28) and the transfer of the proton from the Lys41 is almost complete (Lys41-H BO 0.87). In the product state a proton has been transferred from Lys41 to the O2' position of the sugar. The role of Lys41 as the catalytic acid is a result of the relative positioning of the Lys41 and His12 in the catalytic site. This configuration is supported by calculations and docking studies.

Computing the optimal path in stochastic dynamical systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bauver, Martha; Forgoston, Eric, E-mail: eric.forgoston@montclair.edu; Billings, Lora

2016-08-15

In stochastic systems, one is often interested in finding the optimal path that maximizes the probability of escape from a metastable state or of switching between metastable states. Even for simple systems, it may be impossible to find an analytic form of the optimal path, and in high-dimensional systems, this is almost always the case. In this article, we formulate a constructive methodology that is used to compute the optimal path numerically. The method utilizes finite-time Lyapunov exponents, statistical selection criteria, and a Newton-based iterative minimizing scheme. The method is applied to four examples. The first example is a two-dimensionalmore » system that describes a single population with internal noise. This model has an analytical solution for the optimal path. The numerical solution found using our computational method agrees well with the analytical result. The second example is a more complicated four-dimensional system where our numerical method must be used to find the optimal path. The third example, although a seemingly simple two-dimensional system, demonstrates the success of our method in finding the optimal path where other numerical methods are known to fail. In the fourth example, the optimal path lies in six-dimensional space and demonstrates the power of our method in computing paths in higher-dimensional spaces.« less

Kinetics of enzymatic trans-esterification of glycerides for biodiesel production.

PubMed

Calabrò, Vincenza; Ricca, Emanuele; De Paola, Maria Gabriela; Curcio, Stefano; Iorio, Gabriele

2010-08-01

In this paper, the reaction of enzymatic trans-esterification of glycerides with ethanol in a reaction medium containing hexane at a temperature of 37 degrees C has been studied. The enzyme was Lipase from Mucor miehei, immobilized on ionic exchange resin, aimed at achieving high catalytic specific surface and recovering, regenerating and reusing the biocatalyst. A kinetic analysis has been carried out to identify the reaction path; the rate equation and kinetic parameters have been also calculated. The kinetic model has been validated by comparison between predicted and experimental results. Mass transport resistances estimation was undertaken in order to verify that the kinetics found was intrinsic. Model potentialities in terms of reactors design and optimization are also shown.

Free Energy Contribution Analysis Using Response Kernel Approximation: Insights into the Acylation Reaction of a Beta-Lactamase.

PubMed

Asada, Toshio; Ando, Kanta; Bandyopadhyay, Pradipta; Koseki, Shiro

2016-09-08

A widely applicable free energy contribution analysis (FECA) method based on the quantum mechanical/molecular mechanical (QM/MM) approximation using response kernel approaches has been proposed to investigate the influences of environmental residues and/or atoms in the QM region on the free energy profile. This method can evaluate atomic contributions to the free energy along the reaction path including polarization effects on the QM region within a dramatically reduced computational time. The rate-limiting step in the deactivation of the β-lactam antibiotic cefalotin (CLS) by β-lactamase was studied using this method. The experimentally observed activation barrier was successfully reproduced by free energy perturbation calculations along the optimized reaction path that involved activation by the carboxylate moiety in CLS. It was found that the free energy profile in the QM region was slightly higher than the isolated energy and that two residues, Lys67 and Lys315, as well as water molecules deeply influenced the QM atoms associated with the bond alternation reaction in the acyl-enzyme intermediate. These facts suggested that the surrounding residues are favorable for the reactant complex and prevent the intermediate from being too stabilized to proceed to the following deacylation reaction. We have demonstrated that the free energy contribution analysis should be a useful method to investigate enzyme catalysis and to facilitate intelligent molecular design.

Exploring the full catalytic cycle of rhodium(i)–BINAP-catalysed isomerisation of allylic amines: a graph theory approach for path optimisation† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc00401j Click here for additional data file.

PubMed Central

Yoshimura, Takayoshi; Taketsugu, Tetsuya; Sawamura, Masaya

2017-01-01

We explored the reaction mechanism of the cationic rhodium(i)–BINAP complex catalysed isomerisation of allylic amines using the artificial force induced reaction method with the global reaction route mapping strategy, which enabled us to search for various reaction paths without assumption of transition states. The entire reaction network was reproduced in the form of a graph, and reasonable paths were selected from the complicated network using Prim’s algorithm. As a result, a new dissociative reaction mechanism was proposed. Our comprehensive reaction path search provided rationales for the E/Z and S/R selectivities of the stereoselective reaction. PMID:28970877

Energy Optimal Path Planning: Integrating Coastal Ocean Modelling with Optimal Control

NASA Astrophysics Data System (ADS)

Subramani, D. N.; Haley, P. J., Jr.; Lermusiaux, P. F. J.

2016-02-01

A stochastic optimization methodology is formulated for computing energy-optimal paths from among time-optimal paths of autonomous vehicles navigating in a dynamic flow field. To set up the energy optimization, the relative vehicle speed and headings are considered to be stochastic, and new stochastic Dynamically Orthogonal (DO) level-set equations that govern their stochastic time-optimal reachability fronts are derived. Their solution provides the distribution of time-optimal reachability fronts and corresponding distribution of time-optimal paths. An optimization is then performed on the vehicle's energy-time joint distribution to select the energy-optimal paths for each arrival time, among all stochastic time-optimal paths for that arrival time. The accuracy and efficiency of the DO level-set equations for solving the governing stochastic level-set reachability fronts are quantitatively assessed, including comparisons with independent semi-analytical solutions. Energy-optimal missions are studied in wind-driven barotropic quasi-geostrophic double-gyre circulations, and in realistic data-assimilative re-analyses of multiscale coastal ocean flows. The latter re-analyses are obtained from multi-resolution 2-way nested primitive-equation simulations of tidal-to-mesoscale dynamics in the Middle Atlantic Bight and Shelbreak Front region. The effects of tidal currents, strong wind events, coastal jets, and shelfbreak fronts on the energy-optimal paths are illustrated and quantified. Results showcase the opportunities for longer-duration missions that intelligently utilize the ocean environment to save energy, rigorously integrating ocean forecasting with optimal control of autonomous vehicles.

Application of particle swarm optimization in path planning of mobile robot

NASA Astrophysics Data System (ADS)

Wang, Yong; Cai, Feng; Wang, Ying

2017-08-01

In order to realize the optimal path planning of mobile robot in unknown environment, a particle swarm optimization algorithm based on path length as fitness function is proposed. The location of the global optimal particle is determined by the minimum fitness value, and the robot moves along the points of the optimal particles to the target position. The process of moving to the target point is done with MATLAB R2014a. Compared with the standard particle swarm optimization algorithm, the simulation results show that this method can effectively avoid all obstacles and get the optimal path.

Imaging Molecular Motion: Femtosecond X-Ray Scattering of an Electrocyclic Chemical Reaction

NASA Astrophysics Data System (ADS)

Minitti, M. P.; Budarz, J. M.; Kirrander, A.; Robinson, J. S.; Ratner, D.; Lane, T. J.; Zhu, D.; Glownia, J. M.; Kozina, M.; Lemke, H. T.; Sikorski, M.; Feng, Y.; Nelson, S.; Saita, K.; Stankus, B.; Northey, T.; Hastings, J. B.; Weber, P. M.

2015-06-01

Structural rearrangements within single molecules occur on ultrafast time scales. Many aspects of molecular dynamics, such as the energy flow through excited states, have been studied using spectroscopic techniques, yet the goal to watch molecules evolve their geometrical structure in real time remains challenging. By mapping nuclear motions using femtosecond x-ray pulses, we have created real-space representations of the evolving dynamics during a well-known chemical reaction and show a series of time-sorted structural snapshots produced by ultrafast time-resolved hard x-ray scattering. A computational analysis optimally matches the series of scattering patterns produced by the x rays to a multitude of potential reaction paths. In so doing, we have made a critical step toward the goal of viewing chemical reactions on femtosecond time scales, opening a new direction in studies of ultrafast chemical reactions in the gas phase.

Imaging Molecular Motion: Femtosecond X-Ray Scattering of an Electrocyclic Chemical Reaction.

PubMed

Minitti, M P; Budarz, J M; Kirrander, A; Robinson, J S; Ratner, D; Lane, T J; Zhu, D; Glownia, J M; Kozina, M; Lemke, H T; Sikorski, M; Feng, Y; Nelson, S; Saita, K; Stankus, B; Northey, T; Hastings, J B; Weber, P M

2015-06-26

Structural rearrangements within single molecules occur on ultrafast time scales. Many aspects of molecular dynamics, such as the energy flow through excited states, have been studied using spectroscopic techniques, yet the goal to watch molecules evolve their geometrical structure in real time remains challenging. By mapping nuclear motions using femtosecond x-ray pulses, we have created real-space representations of the evolving dynamics during a well-known chemical reaction and show a series of time-sorted structural snapshots produced by ultrafast time-resolved hard x-ray scattering. A computational analysis optimally matches the series of scattering patterns produced by the x rays to a multitude of potential reaction paths. In so doing, we have made a critical step toward the goal of viewing chemical reactions on femtosecond time scales, opening a new direction in studies of ultrafast chemical reactions in the gas phase.

A benchmark for reaction coordinates in the transition path ensemble

PubMed Central

2016-01-01

The molecular mechanism of a reaction is embedded in its transition path ensemble, the complete collection of reactive trajectories. Utilizing the information in the transition path ensemble alone, we developed a novel metric, which we termed the emergent potential energy, for distinguishing reaction coordinates from the bath modes. The emergent potential energy can be understood as the average energy cost for making a displacement of a coordinate in the transition path ensemble. Where displacing a bath mode invokes essentially no cost, it costs significantly to move the reaction coordinate. Based on some general assumptions of the behaviors of reaction and bath coordinates in the transition path ensemble, we proved theoretically with statistical mechanics that the emergent potential energy could serve as a benchmark of reaction coordinates and demonstrated its effectiveness by applying it to a prototypical system of biomolecular dynamics. Using the emergent potential energy as guidance, we developed a committor-free and intuition-independent method for identifying reaction coordinates in complex systems. We expect this method to be applicable to a wide range of reaction processes in complex biomolecular systems. PMID:27059559

Computationally efficient characterization of potential energy surfaces based on fingerprint distances

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schaefer, Bastian; Goedecker, Stefan, E-mail: stefan.goedecker@unibas.ch

2016-07-21

An analysis of the network defined by the potential energy minima of multi-atomic systems and their connectivity via reaction pathways that go through transition states allows us to understand important characteristics like thermodynamic, dynamic, and structural properties. Unfortunately computing the transition states and reaction pathways in addition to the significant energetically low-lying local minima is a computationally demanding task. We here introduce a computationally efficient method that is based on a combination of the minima hopping global optimization method and the insight that uphill barriers tend to increase with increasing structural distances of the educt and product states. This methodmore » allows us to replace the exact connectivity information and transition state energies with alternative and approximate concepts. Without adding any significant additional cost to the minima hopping global optimization approach, this method allows us to generate an approximate network of the minima, their connectivity, and a rough measure for the energy needed for their interconversion. This can be used to obtain a first qualitative idea on important physical and chemical properties by means of a disconnectivity graph analysis. Besides the physical insight obtained by such an analysis, the gained knowledge can be used to make a decision if it is worthwhile or not to invest computational resources for an exact computation of the transition states and the reaction pathways. Furthermore it is demonstrated that the here presented method can be used for finding physically reasonable interconversion pathways that are promising input pathways for methods like transition path sampling or discrete path sampling.« less

On computing the global time-optimal motions of robotic manipulators in the presence of obstacles

NASA Technical Reports Server (NTRS)

Shiller, Zvi; Dubowsky, Steven

1991-01-01

A method for computing the time-optimal motions of robotic manipulators is presented that considers the nonlinear manipulator dynamics, actuator constraints, joint limits, and obstacles. The optimization problem is reduced to a search for the time-optimal path in the n-dimensional position space. A small set of near-optimal paths is first efficiently selected from a grid, using a branch and bound search and a series of lower bound estimates on the traveling time along a given path. These paths are further optimized with a local path optimization to yield the global optimal solution. Obstacles are considered by eliminating the collision points from the tessellated space and by adding a penalty function to the motion time in the local optimization. The computational efficiency of the method stems from the reduced dimensionality of the searched spaced and from combining the grid search with a local optimization. The method is demonstrated in several examples for two- and six-degree-of-freedom manipulators with obstacles.

Electronic excited state paths of Stone-Wales rearrangement in pyrene: roles of conical intersections.

PubMed

Yamazaki, Kaoru; Niitsu, Naoyuki; Nakamura, Kosuke; Kanno, Manabu; Kono, Hirohiko

2012-11-26

We investigated the reaction paths of Stone-Wales rearrangement (SWR), i.e., π/2 rotation of two carbon atoms with respect to the midpoint of the bond, in graphene and carbon nanotube quantum chemically. Our particular attention is focused on the roles of electronic excitations and conical intersections (CIs) in the reaction mechanism. We used pyrene as a model system. The reaction paths were determined by constructing potential energy surfaces at the MS-CASPT2//SA-CASSCF level of theory. We found that there are no CIs involved in SWR when both of C-C bond cleavage and formation occur simultaneously (concerted mechanism). In contrast, for the reaction path with stepwise cleavage and formation of C-C bonds, C-C bond breaking and making processes proceed through two CIs. When SWR starts from the ground (S(0)) state, the concerted and stepwise paths have an equivalent reaction barrier ΔE(‡) (9.5-9.6 eV). For the reaction path starting from excited states, only the stepwise mechanism is energetically preferable. This path contains a nonadabatic transition between the S(1) and S(0) states via a CI associated with the first stage of C-C bond cleavage and has ΔE(‡) as large as in the S(0) paths. We confirmed that the main active molecular orbitals and electron configurations for the low-lying electronic states of larger nanocarbons are the same as those in pyrene. This result suggests the importance of the nonadiabatic transitions through CIs in the photochemical reactions in large nanocarbons.

Optimization of educational paths for higher education

NASA Astrophysics Data System (ADS)

Tarasyev, Alexandr A.; Agarkov, Gavriil; Medvedev, Aleksandr

2017-11-01

In our research, we combine the theory of economic behavior and the methodology of increasing efficiency of the human capital to estimate the optimal educational paths. We provide an optimization model for higher education process to analyze possible educational paths for each rational individual. The preferences of each rational individual are compared to the best economically possible educational path. The main factor of the individual choice, which is formed by the formation of optimal educational path, deals with higher salaries level in the chosen economic sector after graduation. Another factor that influences on the economic profit is the reduction of educational costs or the possibility of the budget support for the student. The main outcome of this research consists in correction of the governmental policy of investment in human capital based on the results of educational paths optimal control.

Distribution path robust optimization of electric vehicle with multiple distribution centers

PubMed Central

Hao, Wei; He, Ruichun; Jia, Xiaoyan; Pan, Fuquan; Fan, Jing; Xiong, Ruiqi

2018-01-01

To identify electrical vehicle (EV) distribution paths with high robustness, insensitivity to uncertainty factors, and detailed road-by-road schemes, optimization of the distribution path problem of EV with multiple distribution centers and considering the charging facilities is necessary. With the minimum transport time as the goal, a robust optimization model of EV distribution path with adjustable robustness is established based on Bertsimas’ theory of robust discrete optimization. An enhanced three-segment genetic algorithm is also developed to solve the model, such that the optimal distribution scheme initially contains all road-by-road path data using the three-segment mixed coding and decoding method. During genetic manipulation, different interlacing and mutation operations are carried out on different chromosomes, while, during population evolution, the infeasible solution is naturally avoided. A part of the road network of Xifeng District in Qingyang City is taken as an example to test the model and the algorithm in this study, and the concrete transportation paths are utilized in the final distribution scheme. Therefore, more robust EV distribution paths with multiple distribution centers can be obtained using the robust optimization model. PMID:29518169

Efficient sampling of parsimonious inversion histories with application to genome rearrangement in Yersinia.

PubMed

Miklós, István; Darling, Aaron E

2009-06-22

Inversions are among the most common mutations acting on the order and orientation of genes in a genome, and polynomial-time algorithms exist to obtain a minimal length series of inversions that transform one genome arrangement to another. However, the minimum length series of inversions (the optimal sorting path) is often not unique as many such optimal sorting paths exist. If we assume that all optimal sorting paths are equally likely, then statistical inference on genome arrangement history must account for all such sorting paths and not just a single estimate. No deterministic polynomial algorithm is known to count the number of optimal sorting paths nor sample from the uniform distribution of optimal sorting paths. Here, we propose a stochastic method that uniformly samples the set of all optimal sorting paths. Our method uses a novel formulation of parallel Markov chain Monte Carlo. In practice, our method can quickly estimate the total number of optimal sorting paths. We introduce a variant of our approach in which short inversions are modeled to be more likely, and we show how the method can be used to estimate the distribution of inversion lengths and breakpoint usage in pathogenic Yersinia pestis. The proposed method has been implemented in a program called "MC4Inversion." We draw comparison of MC4Inversion to the sampler implemented in BADGER and a previously described importance sampling (IS) technique. We find that on high-divergence data sets, MC4Inversion finds more optimal sorting paths per second than BADGER and the IS technique and simultaneously avoids bias inherent in the IS technique.

JPL-ANTOPT antenna structure optimization program

NASA Technical Reports Server (NTRS)

Strain, D. M.

1994-01-01

New antenna path-length error and pointing-error structure optimization codes were recently added to the MSC/NASTRAN structural analysis computer program. Path-length and pointing errors are important measured of structure-related antenna performance. The path-length and pointing errors are treated as scalar displacements for statics loading cases. These scalar displacements can be subject to constraint during the optimization process. Path-length and pointing-error calculations supplement the other optimization and sensitivity capabilities of NASTRAN. The analysis and design functions were implemented as 'DMAP ALTERs' to the Design Optimization (SOL 200) Solution Sequence of MSC-NASTRAN, Version 67.5.

Three-Dimensional Path Planning for Uninhabited Combat Aerial Vehicle Based on Predator-Prey Pigeon-Inspired Optimization in Dynamic Environment.

PubMed

Zhang, Bo; Duan, Haibin

2017-01-01

Three-dimension path planning of uninhabited combat aerial vehicle (UCAV) is a complicated optimal problem, which mainly focused on optimizing the flight route considering the different types of constrains under complex combating environment. A novel predator-prey pigeon-inspired optimization (PPPIO) is proposed to solve the UCAV three-dimension path planning problem in dynamic environment. Pigeon-inspired optimization (PIO) is a new bio-inspired optimization algorithm. In this algorithm, map and compass operator model and landmark operator model are used to search the best result of a function. The prey-predator concept is adopted to improve global best properties and enhance the convergence speed. The characteristics of the optimal path are presented in the form of a cost function. The comparative simulation results show that our proposed PPPIO algorithm is more efficient than the basic PIO, particle swarm optimization (PSO), and different evolution (DE) in solving UCAV three-dimensional path planning problems.

From the physics of interacting polymers to optimizing routes on the London Underground

PubMed Central

Yeung, Chi Ho; Saad, David; Wong, K. Y. Michael

2013-01-01

Optimizing paths on networks is crucial for many applications, ranging from subway traffic to Internet communication. Because global path optimization that takes account of all path choices simultaneously is computationally hard, most existing routing algorithms optimize paths individually, thus providing suboptimal solutions. We use the physics of interacting polymers and disordered systems to analyze macroscopic properties of generic path optimization problems and derive a simple, principled, generic, and distributed routing algorithm capable of considering all individual path choices simultaneously. We demonstrate the efficacy of the algorithm by applying it to: (i) random graphs resembling Internet overlay networks, (ii) travel on the London Underground network based on Oyster card data, and (iii) the global airport network. Analytically derived macroscopic properties give rise to insightful new routing phenomena, including phase transitions and scaling laws, that facilitate better understanding of the appropriate operational regimes and their limitations, which are difficult to obtain otherwise. PMID:23898198

From the physics of interacting polymers to optimizing routes on the London Underground.

PubMed

Yeung, Chi Ho; Saad, David; Wong, K Y Michael

2013-08-20

Optimizing paths on networks is crucial for many applications, ranging from subway traffic to Internet communication. Because global path optimization that takes account of all path choices simultaneously is computationally hard, most existing routing algorithms optimize paths individually, thus providing suboptimal solutions. We use the physics of interacting polymers and disordered systems to analyze macroscopic properties of generic path optimization problems and derive a simple, principled, generic, and distributed routing algorithm capable of considering all individual path choices simultaneously. We demonstrate the efficacy of the algorithm by applying it to: (i) random graphs resembling Internet overlay networks, (ii) travel on the London Underground network based on Oyster card data, and (iii) the global airport network. Analytically derived macroscopic properties give rise to insightful new routing phenomena, including phase transitions and scaling laws, that facilitate better understanding of the appropriate operational regimes and their limitations, which are difficult to obtain otherwise.

Energy-Aware Multipath Routing Scheme Based on Particle Swarm Optimization in Mobile Ad Hoc Networks

PubMed Central

Robinson, Y. Harold; Rajaram, M.

2015-01-01

Mobile ad hoc network (MANET) is a collection of autonomous mobile nodes forming an ad hoc network without fixed infrastructure. Dynamic topology property of MANET may degrade the performance of the network. However, multipath selection is a great challenging task to improve the network lifetime. We proposed an energy-aware multipath routing scheme based on particle swarm optimization (EMPSO) that uses continuous time recurrent neural network (CTRNN) to solve optimization problems. CTRNN finds the optimal loop-free paths to solve link disjoint paths in a MANET. The CTRNN is used as an optimum path selection technique that produces a set of optimal paths between source and destination. In CTRNN, particle swarm optimization (PSO) method is primly used for training the RNN. The proposed scheme uses the reliability measures such as transmission cost, energy factor, and the optimal traffic ratio between source and destination to increase routing performance. In this scheme, optimal loop-free paths can be found using PSO to seek better link quality nodes in route discovery phase. PSO optimizes a problem by iteratively trying to get a better solution with regard to a measure of quality. The proposed scheme discovers multiple loop-free paths by using PSO technique. PMID:26819966

Enzymatic reaction paths as determined by transition path sampling

NASA Astrophysics Data System (ADS)

Masterson, Jean Emily

Enzymes are biological catalysts capable of enhancing the rates of chemical reactions by many orders of magnitude as compared to solution chemistry. Since the catalytic power of enzymes routinely exceeds that of the best artificial catalysts available, there is much interest in understanding the complete nature of chemical barrier crossing in enzymatic reactions. Two specific questions pertaining to the source of enzymatic rate enhancements are investigated in this work. The first is the issue of how fast protein motions of an enzyme contribute to chemical barrier crossing. Our group has previously identified sub-picosecond protein motions, termed promoting vibrations (PVs), that dynamically modulate chemical transformation in several enzymes. In the case of human heart lactate dehydrogenase (hhLDH), prior studies have shown that a specific axis of residues undergoes a compressional fluctuation towards the active site, decreasing a hydride and a proton donor--acceptor distance on a sub-picosecond timescale to promote particle transfer. To more thoroughly understand the contribution of this dynamic motion to the enzymatic reaction coordinate of hhLDH, we conducted transition path sampling (TPS) using four versions of the enzymatic system: a wild type enzyme with natural isotopic abundance; a heavy enzyme where all the carbons, nitrogens, and non-exchangeable hydrogens were replaced with heavy isotopes; and two versions of the enzyme with mutations in the axis of PV residues. We generated four separate ensembles of reaction paths and analyzed each in terms of the reaction mechanism, time of barrier crossing, dynamics of the PV, and residues involved in the enzymatic reaction coordinate. We found that heavy isotopic substitution of hhLDH altered the sub-picosecond dynamics of the PV, changed the favored reaction mechanism, dramatically increased the time of barrier crossing, but did not have an effect on the specific residues involved in the PV. In the mutant systems, we observed changes in the reaction mechanism and altered contributions of the mutated residues to the enzymatic reaction coordinate, but we did not detect a substantial change in the time of barrier crossing. These results confirm the importance of maintaining the dynamics and structural scaffolding of the hhLDH PV in order to facilitate facile barrier passage. We also utilized TPS to investigate the possible role of fast protein dynamics in the enzymatic reaction coordinate of human dihydrofolate reductase (hsDHFR). We found that sub-picosecond dynamics of hsDHFR do contribute to the reaction coordinate, whereas this is not the case in the E. coli version of the enzyme. This result indicates a shift in the DHFR family to a more dynamic version of catalysis. The second inquiry we addressed in this thesis regarding enzymatic barrier passage concerns the variability of paths through reactive phase space for a given enzymatic reaction. We further investigated the hhLDH-catalyzed reaction using a high-perturbation TPS algorithm. Though we saw that alternate reaction paths were possible, the dominant reaction path we observed corresponded to that previously elucidated in prior hhLDH TPS studies. Since the additional reaction paths we observed were likely high-energy, these results indicate that only the dominant reaction path contributes significantly to the overall reaction rate. In conclusion, we show that the enzymes hhLDH and hsDHFR exhibit paths through reactive phase space where fast protein motions are involved in the enzymatic reaction coordinate and exhibit a non-negligible contribution to chemical barrier crossing.

Efficient Sampling of Parsimonious Inversion Histories with Application to Genome Rearrangement in Yersinia

PubMed Central

Darling, Aaron E.

2009-01-01

Inversions are among the most common mutations acting on the order and orientation of genes in a genome, and polynomial-time algorithms exist to obtain a minimal length series of inversions that transform one genome arrangement to another. However, the minimum length series of inversions (the optimal sorting path) is often not unique as many such optimal sorting paths exist. If we assume that all optimal sorting paths are equally likely, then statistical inference on genome arrangement history must account for all such sorting paths and not just a single estimate. No deterministic polynomial algorithm is known to count the number of optimal sorting paths nor sample from the uniform distribution of optimal sorting paths. Here, we propose a stochastic method that uniformly samples the set of all optimal sorting paths. Our method uses a novel formulation of parallel Markov chain Monte Carlo. In practice, our method can quickly estimate the total number of optimal sorting paths. We introduce a variant of our approach in which short inversions are modeled to be more likely, and we show how the method can be used to estimate the distribution of inversion lengths and breakpoint usage in pathogenic Yersinia pestis. The proposed method has been implemented in a program called “MC4Inversion.” We draw comparison of MC4Inversion to the sampler implemented in BADGER and a previously described importance sampling (IS) technique. We find that on high-divergence data sets, MC4Inversion finds more optimal sorting paths per second than BADGER and the IS technique and simultaneously avoids bias inherent in the IS technique. PMID:20333186

Effect of a limited-enforcement intelligent tutoring system in dermatopathology on student errors, goals and solution paths.

PubMed

Payne, Velma L; Medvedeva, Olga; Legowski, Elizabeth; Castine, Melissa; Tseytlin, Eugene; Jukic, Drazen; Crowley, Rebecca S

2009-11-01

Determine effects of a limited-enforcement intelligent tutoring system in dermatopathology on student errors, goals and solution paths. Determine if limited enforcement in a medical tutoring system inhibits students from learning the optimal and most efficient solution path. Describe the type of deviations from the optimal solution path that occur during tutoring, and how these deviations change over time. Determine if the size of the problem-space (domain scope), has an effect on learning gains when using a tutor with limited enforcement. Analyzed data mined from 44 pathology residents using SlideTutor-a Medical Intelligent Tutoring System in Dermatopathology that teaches histopathologic diagnosis and reporting skills based on commonly used diagnostic algorithms. Two subdomains were included in the study representing sub-algorithms of different sizes and complexities. Effects of the tutoring system on student errors, goal states and solution paths were determined. Students gradually increase the frequency of steps that match the tutoring system's expectation of expert performance. Frequency of errors gradually declines in all categories of error significance. Student performance frequently differs from the tutor-defined optimal path. However, as students continue to be tutored, they approach the optimal solution path. Performance in both subdomains was similar for both errors and goal differences. However, the rate at which students progress toward the optimal solution path differs between the two domains. Tutoring in superficial perivascular dermatitis, the larger and more complex domain was associated with a slower rate of approximation towards the optimal solution path. Students benefit from a limited-enforcement tutoring system that leverages diagnostic algorithms but does not prevent alternative strategies. Even with limited enforcement, students converge toward the optimal solution path.

An improved multi-paths optimization method for video stabilization

NASA Astrophysics Data System (ADS)

Qin, Tao; Zhong, Sheng

2018-03-01

For video stabilization, the difference between original camera motion path and the optimized one is proportional to the cropping ratio and warping ratio. A good optimized path should preserve the moving tendency of the original one meanwhile the cropping ratio and warping ratio of each frame should be kept in a proper range. In this paper we use an improved warping-based motion representation model, and propose a gauss-based multi-paths optimization method to get a smoothing path and obtain a stabilized video. The proposed video stabilization method consists of two parts: camera motion path estimation and path smoothing. We estimate the perspective transform of adjacent frames according to warping-based motion representation model. It works well on some challenging videos where most previous 2D methods or 3D methods fail for lacking of long features trajectories. The multi-paths optimization method can deal well with parallax, as we calculate the space-time correlation of the adjacent grid, and then a kernel of gauss is used to weigh the motion of adjacent grid. Then the multi-paths are smoothed while minimize the crop ratio and the distortion. We test our method on a large variety of consumer videos, which have casual jitter and parallax, and achieve good results.

Efficient approach to include molecular polarizations using charge and atom dipole response kernels to calculate free energy gradients in the QM/MM scheme.

PubMed

Asada, Toshio; Ando, Kanta; Sakurai, Koji; Koseki, Shiro; Nagaoka, Masataka

2015-10-28

An efficient approach to evaluate free energy gradients (FEGs) within the quantum mechanical/molecular mechanical (QM/MM) framework has been proposed to clarify reaction processes on the free energy surface (FES) in molecular assemblies. The method is based on response kernel approximations denoted as the charge and the atom dipole response kernel (CDRK) model that include explicitly induced atom dipoles. The CDRK model was able to reproduce polarization effects for both electrostatic interactions between QM and MM regions and internal energies in the QM region obtained by conventional QM/MM methods. In contrast to charge response kernel (CRK) models, CDRK models could be applied to various kinds of molecules, even linear or planer molecules, without using imaginary interaction sites. Use of the CDRK model enabled us to obtain FEGs on QM atoms in significantly reduced computational time. It was also clearly demonstrated that the time development of QM forces of the solvated propylene carbonate radical cation (PC˙(+)) provided reliable results for 1 ns molecular dynamics (MD) simulation, which were quantitatively in good agreement with expensive QM/MM results. Using FEG and nudged elastic band (NEB) methods, we found two optimized reaction paths on the FES for decomposition reactions to generate CO2 molecules from PC˙(+), whose reaction is known as one of the degradation mechanisms in the lithium-ion battery. Two of these reactions proceed through an identical intermediate structure whose molecular dipole moment is larger than that of the reactant to be stabilized in the solvent, which has a high relative dielectric constant. Thus, in order to prevent decomposition reactions, PC˙(+) should be modified to have a smaller dipole moment along two reaction paths.

Research on cutting path optimization of sheet metal parts based on ant colony algorithm

NASA Astrophysics Data System (ADS)

Wu, Z. Y.; Ling, H.; Li, L.; Wu, L. H.; Liu, N. B.

2017-09-01

In view of the disadvantages of the current cutting path optimization methods of sheet metal parts, a new method based on ant colony algorithm was proposed in this paper. The cutting path optimization problem of sheet metal parts was taken as the research object. The essence and optimization goal of the optimization problem were presented. The traditional serial cutting constraint rule was improved. The cutting constraint rule with cross cutting was proposed. The contour lines of parts were discretized and the mathematical model of cutting path optimization was established. Thus the problem was converted into the selection problem of contour lines of parts. Ant colony algorithm was used to solve the problem. The principle and steps of the algorithm were analyzed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reister, D.B.

This paper uses the Pontryagin maximum principle to find time optimal paths for a constant speed unicycle. The time optimal paths consist of sequences of arcs of circles and straight lines. The maximum principle introduced concepts (dual variables, bang-bang solutions, singular solutions, and transversality conditions) that provide important insight into the nature of the time optimal paths. 10 refs., 6 figs.

A taxonomy of integral reaction path analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grcar, Joseph F.; Day, Marcus S.; Bell, John B.

2004-12-23

W. C. Gardiner observed that achieving understanding through combustion modeling is limited by the ability to recognize the implications of what has been computed and to draw conclusions about the elementary steps underlying the reaction mechanism. This difficulty can be overcome in part by making better use of reaction path analysis in the context of multidimensional flame simulations. Following a survey of current practice, an integral reaction flux is formulated in terms of conserved scalars that can be calculated in a fully automated way. Conditional analyses are then introduced, and a taxonomy for bidirectional path analysis is explored. Many examplesmore » illustrate the resulting path analysis and uncover some new results about nonpremixed methane-air laminar jets.« less

Finding Chemical Reaction Paths with a Multilevel Preconditioning Protocol

PubMed Central

2015-01-01

Finding transition paths for chemical reactions can be computationally costly owing to the level of quantum-chemical theory needed for accuracy. Here, we show that a multilevel preconditioning scheme that was recently introduced (Tempkin et al. J. Chem. Phys.2014, 140, 184114) can be used to accelerate quantum-chemical string calculations. We demonstrate the method by finding minimum-energy paths for two well-characterized reactions: tautomerization of malonaldehyde and Claissen rearrangement of chorismate to prephanate. For these reactions, we show that preconditioning density functional theory (DFT) with a semiempirical method reduces the computational cost for reaching a converged path that is an optimum under DFT by several fold. The approach also shows promise for free energy calculations when thermal noise can be controlled. PMID:25516726

Variational nature, integration, and properties of Newton reaction path

NASA Astrophysics Data System (ADS)

Bofill, Josep Maria; Quapp, Wolfgang

2011-02-01

The distinguished coordinate path and the reduced gradient following path or its equivalent formulation, the Newton trajectory, are analyzed and unified using the theory of calculus of variations. It is shown that their minimum character is related to the fact that the curve is located in a valley region. In this case, we say that the Newton trajectory is a reaction path with the category of minimum energy path. In addition to these findings a Runge-Kutta-Fehlberg algorithm to integrate these curves is also proposed.

Variational nature, integration, and properties of Newton reaction path.

PubMed

Bofill, Josep Maria; Quapp, Wolfgang

2011-02-21

The distinguished coordinate path and the reduced gradient following path or its equivalent formulation, the Newton trajectory, are analyzed and unified using the theory of calculus of variations. It is shown that their minimum character is related to the fact that the curve is located in a valley region. In this case, we say that the Newton trajectory is a reaction path with the category of minimum energy path. In addition to these findings a Runge-Kutta-Fehlberg algorithm to integrate these curves is also proposed.

Optimal impulsive time-fixed orbital rendezvous and interception with path constraints

NASA Technical Reports Server (NTRS)

Taur, D.-R.; Prussing, J. E.; Coverstone-Carroll, V.

1990-01-01

Minimum-fuel, impulsive, time-fixed solutions are obtained for the problem of orbital rendezvous and interception with interior path constraints. Transfers between coplanar circular orbits in an inverse-square gravitational field are considered, subject to a circular path constraint representing a minimum or maximum permissible orbital radius. Primer vector theory is extended to incorporate path constraints. The optimal number of impulses, their times and positions, and the presence of initial or final coasting arcs are determined. The existence of constraint boundary arcs and boundary points is investigated as well as the optimality of a class of singular arc solutions. To illustrate the complexities introduced by path constraints, an analysis is made of optimal rendezvous in field-free space subject to a minimum radius constraint.

MapMaker and PathTracer for tracking carbon in genome-scale metabolic models

PubMed Central

Tervo, Christopher J.; Reed, Jennifer L.

2016-01-01

Constraint-based reconstruction and analysis (COBRA) modeling results can be difficult to interpret given the large numbers of reactions in genome-scale models. While paths in metabolic networks can be found, existing methods are not easily combined with constraint-based approaches. To address this limitation, two tools (MapMaker and PathTracer) were developed to find paths (including cycles) between metabolites, where each step transfers carbon from reactant to product. MapMaker predicts carbon transfer maps (CTMs) between metabolites using only information on molecular formulae and reaction stoichiometry, effectively determining which reactants and products share carbon atoms. MapMaker correctly assigned CTMs for over 97% of the 2,251 reactions in an Escherichia coli metabolic model (iJO1366). Using CTMs as inputs, PathTracer finds paths between two metabolites. PathTracer was applied to iJO1366 to investigate the importance of using CTMs and COBRA constraints when enumerating paths, to find active and high flux paths in flux balance analysis (FBA) solutions, to identify paths for putrescine utilization, and to elucidate a potential CO2 fixation pathway in E. coli. These results illustrate how MapMaker and PathTracer can be used in combination with constraint-based models to identify feasible, active, and high flux paths between metabolites. PMID:26771089

Research on NC laser combined cutting optimization model of sheet metal parts

NASA Astrophysics Data System (ADS)

Wu, Z. Y.; Zhang, Y. L.; Li, L.; Wu, L. H.; Liu, N. B.

2017-09-01

The optimization problem for NC laser combined cutting of sheet metal parts was taken as the research object in this paper. The problem included two contents: combined packing optimization and combined cutting path optimization. In the problem of combined packing optimization, the method of “genetic algorithm + gravity center NFP + geometric transformation” was used to optimize the packing of sheet metal parts. In the problem of combined cutting path optimization, the mathematical model of cutting path optimization was established based on the parts cutting constraint rules of internal contour priority and cross cutting. The model played an important role in the optimization calculation of NC laser combined cutting.

A Hybrid Metaheuristic DE/CS Algorithm for UCAV Three-Dimension Path Planning

PubMed Central

Wang, Gaige; Guo, Lihong; Duan, Hong; Wang, Heqi; Liu, Luo; Shao, Mingzhen

2012-01-01

Three-dimension path planning for uninhabited combat air vehicle (UCAV) is a complicated high-dimension optimization problem, which primarily centralizes on optimizing the flight route considering the different kinds of constrains under complicated battle field environments. A new hybrid metaheuristic differential evolution (DE) and cuckoo search (CS) algorithm is proposed to solve the UCAV three-dimension path planning problem. DE is applied to optimize the process of selecting cuckoos of the improved CS model during the process of cuckoo updating in nest. The cuckoos can act as an agent in searching the optimal UCAV path. And then, the UCAV can find the safe path by connecting the chosen nodes of the coordinates while avoiding the threat areas and costing minimum fuel. This new approach can accelerate the global convergence speed while preserving the strong robustness of the basic CS. The realization procedure for this hybrid metaheuristic approach DE/CS is also presented. In order to make the optimized UCAV path more feasible, the B-Spline curve is adopted for smoothing the path. To prove the performance of this proposed hybrid metaheuristic method, it is compared with basic CS algorithm. The experiment shows that the proposed approach is more effective and feasible in UCAV three-dimension path planning than the basic CS model. PMID:23193383

A hybrid metaheuristic DE/CS algorithm for UCAV three-dimension path planning.

PubMed

Wang, Gaige; Guo, Lihong; Duan, Hong; Wang, Heqi; Liu, Luo; Shao, Mingzhen

2012-01-01

Three-dimension path planning for uninhabited combat air vehicle (UCAV) is a complicated high-dimension optimization problem, which primarily centralizes on optimizing the flight route considering the different kinds of constrains under complicated battle field environments. A new hybrid metaheuristic differential evolution (DE) and cuckoo search (CS) algorithm is proposed to solve the UCAV three-dimension path planning problem. DE is applied to optimize the process of selecting cuckoos of the improved CS model during the process of cuckoo updating in nest. The cuckoos can act as an agent in searching the optimal UCAV path. And then, the UCAV can find the safe path by connecting the chosen nodes of the coordinates while avoiding the threat areas and costing minimum fuel. This new approach can accelerate the global convergence speed while preserving the strong robustness of the basic CS. The realization procedure for this hybrid metaheuristic approach DE/CS is also presented. In order to make the optimized UCAV path more feasible, the B-Spline curve is adopted for smoothing the path. To prove the performance of this proposed hybrid metaheuristic method, it is compared with basic CS algorithm. The experiment shows that the proposed approach is more effective and feasible in UCAV three-dimension path planning than the basic CS model.

Surface Navigation Using Optimized Waypoints and Particle Swarm Optimization

NASA Technical Reports Server (NTRS)

Birge, Brian

2013-01-01

The design priority for manned space exploration missions is almost always placed on human safety. Proposed manned surface exploration tasks (lunar, asteroid sample returns, Mars) have the possibility of astronauts traveling several kilometers away from a home base. Deviations from preplanned paths are expected while exploring. In a time-critical emergency situation, there is a need to develop an optimal home base return path. The return path may or may not be similar to the outbound path, and what defines optimal may change with, and even within, each mission. A novel path planning algorithm and prototype program was developed using biologically inspired particle swarm optimization (PSO) that generates an optimal path of traversal while avoiding obstacles. Applications include emergency path planning on lunar, Martian, and/or asteroid surfaces, generating multiple scenarios for outbound missions, Earth-based search and rescue, as well as human manual traversal and/or path integration into robotic control systems. The strategy allows for a changing environment, and can be re-tasked at will and run in real-time situations. Given a random extraterrestrial planetary or small body surface position, the goal was to find the fastest (or shortest) path to an arbitrary position such as a safe zone or geographic objective, subject to possibly varying constraints. The problem requires a workable solution 100% of the time, though it does not require the absolute theoretical optimum. Obstacles should be avoided, but if they cannot be, then the algorithm needs to be smart enough to recognize this and deal with it. With some modifications, it works with non-stationary error topologies as well.

Finding Chemical Reaction Paths with a Multilevel Preconditioning Protocol

DOE PAGES

Kale, Seyit; Sode, Olaseni; Weare, Jonathan; ...

2014-11-07

Finding transition paths for chemical reactions can be computationally costly owing to the level of quantum-chemical theory needed for accuracy. Here, we show that a multilevel preconditioning scheme that was recently introduced (Tempkin et al. J. Chem. Phys. 2014, 140, 184114) can be used to accelerate quantum-chemical string calculations. We demonstrate the method by finding minimum-energy paths for two well-characterized reactions: tautomerization of malonaldehyde and Claissen rearrangement of chorismate to prephanate. For these reactions, we show that preconditioning density functional theory (DFT) with a semiempirical method reduces the computational cost for reaching a converged path that is an optimum undermore » DFT by several fold. In conclusion, the approach also shows promise for free energy calculations when thermal noise can be controlled.« less

Efficient approach to obtain free energy gradient using QM/MM MD simulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asada, Toshio; Koseki, Shiro; The Research Institute for Molecular Electronic Devices

2015-12-31

The efficient computational approach denoted as charge and atom dipole response kernel (CDRK) model to consider polarization effects of the quantum mechanical (QM) region is described using the charge response and the atom dipole response kernels for free energy gradient (FEG) calculations in the quantum mechanical/molecular mechanical (QM/MM) method. CDRK model can reasonably reproduce energies and also energy gradients of QM and MM atoms obtained by expensive QM/MM calculations in a drastically reduced computational time. This model is applied on the acylation reaction in hydrated trypsin-BPTI complex to optimize the reaction path on the free energy surface by means ofmore » FEG and the nudged elastic band (NEB) method.« less

Energy-optimal path planning in the coastal ocean

NASA Astrophysics Data System (ADS)

Subramani, Deepak N.; Haley, Patrick J.; Lermusiaux, Pierre F. J.

2017-05-01

We integrate data-driven ocean modeling with the stochastic Dynamically Orthogonal (DO) level-set optimization methodology to compute and study energy-optimal paths, speeds, and headings for ocean vehicles in the Middle-Atlantic Bight (MAB) region. We hindcast the energy-optimal paths from among exact time-optimal paths for the period 28 August 2006 to 9 September 2006. To do so, we first obtain a data-assimilative multiscale reanalysis, combining ocean observations with implicit two-way nested multiresolution primitive-equation simulations of the tidal-to-mesoscale dynamics in the region. Second, we solve the reduced-order stochastic DO level-set partial differential equations (PDEs) to compute the joint probability of minimum arrival time, vehicle-speed time series, and total energy utilized. Third, for each arrival time, we select the vehicle-speed time series that minimize the total energy utilization from the marginal probability of vehicle-speed and total energy. The corresponding energy-optimal path and headings are obtained through the exact particle-backtracking equation. Theoretically, the present methodology is PDE-based and provides fundamental energy-optimal predictions without heuristics. Computationally, it is 3-4 orders of magnitude faster than direct Monte Carlo methods. For the missions considered, we analyze the effects of the regional tidal currents, strong wind events, coastal jets, shelfbreak front, and other local circulations on the energy-optimal paths. Results showcase the opportunities for vehicles that intelligently utilize the ocean environment to minimize energy usage, rigorously integrating ocean forecasting with optimal control of autonomous vehicles.

Density function theoretical study on the complex involved in Th atom-activated C-C bond in C2H6

NASA Astrophysics Data System (ADS)

Qing-Qing, Wang; Peng, Li; Tao, Gao; Hong-Yan, Wang; Bing-Yun, Ao

2016-06-01

Density functional theory (DFT) calculations are performed to investigate the reactivity of Th atom toward ethane C-C bond activation. A comprehensive description of the reaction mechanisms leading to two different reaction products is presented. We report a complete exploration of the potential energy surfaces by taking into consideration different spin states. In addition, the intermediate and transition states along the reaction paths are characterized. Total, partial, and overlap population density of state diagrams and analyses are also presented. Furthermore, the natures of the chemical bonding of intermediate and transition states are studied by using topological method combined with electron localization function (ELF) and Mayer bond order. Infrared spectrum (IR) is obtained and further discussed based on the optimized geometries. Project supported by the National Natural Science Foundation of China (Grant Nos. 21371160, 21401173, and 11364023).

Solid-State Explosive Reaction for Nanoporous Bulk Thermoelectric Materials.

PubMed

Zhao, Kunpeng; Duan, Haozhi; Raghavendra, Nunna; Qiu, Pengfei; Zeng, Yi; Zhang, Wenqing; Yang, Jihui; Shi, Xun; Chen, Lidong

2017-11-01

High-performance thermoelectric materials require ultralow lattice thermal conductivity typically through either shortening the phonon mean free path or reducing the specific heat. Beyond these two approaches, a new unique, simple, yet ultrafast solid-state explosive reaction is proposed to fabricate nanoporous bulk thermoelectric materials with well-controlled pore sizes and distributions to suppress thermal conductivity. By investigating a wide variety of functional materials, general criteria for solid-state explosive reactions are built upon both thermodynamics and kinetics, and then successfully used to tailor material's microstructures and porosity. A drastic decrease in lattice thermal conductivity down below the minimum value of the fully densified materials and enhancement in thermoelectric figure of merit are achieved in porous bulk materials. This work demonstrates that controlling materials' porosity is a very effective strategy and is easy to be combined with other approaches for optimizing thermoelectric performance. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Comparison of Two Path Planners for Planetary Rovers

NASA Technical Reports Server (NTRS)

Tarokh, M.; Shiller, Z.; Hayati, S.

1999-01-01

The paper presents two path planners suitable for planetary rovers. The first is based on fuzzy description of the terrain, and genetic algorithm to find a traversable path in a rugged terrain. The second planner uses a global optimization method with a cost function that is the path distance divided by the velocity limit obtained from the consideration of the rover static and dynamic stability. A description of both methods is provided, and the results of paths produced are given which show the effectiveness of the path planners in finding near optimal paths. The features of the methods and their suitability and application for rover path planning are compared

An engineering optimization method with application to STOL-aircraft approach and landing trajectories

NASA Technical Reports Server (NTRS)

Jacob, H. G.

1972-01-01

An optimization method has been developed that computes the optimal open loop inputs for a dynamical system by observing only its output. The method reduces to static optimization by expressing the inputs as series of functions with parameters to be optimized. Since the method is not concerned with the details of the dynamical system to be optimized, it works for both linear and nonlinear systems. The method and the application to optimizing longitudinal landing paths for a STOL aircraft with an augmented wing are discussed. Noise, fuel, time, and path deviation minimizations are considered with and without angle of attack, acceleration excursion, flight path, endpoint, and other constraints.

Planning minimum-energy paths in an off-road environment with anisotropic traversal costs and motion constraints. Doctoral thesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ross, R.S.

1989-06-01

For a vehicle operating across arbitrarily-contoured terrain, finding the most fuel-efficient route between two points can be viewed as a high-level global path-planning problem with traversal costs and stability dependent on the direction of travel (anisotropic). The problem assumes a two-dimensional polygonal map of homogeneous cost regions for terrain representation constructed from elevation information. The anisotropic energy cost of vehicle motion has a non-braking component dependent on horizontal distance, a braking component dependent on vertical distance, and a constant path-independent component. The behavior of minimum-energy paths is then proved to be restricted to a small, but optimal set of traversalmore » types. An optimal-path-planning algorithm, using a heuristic search technique, reduces the infinite number of paths between the start and goal points to a finite number by generating sequences of goal-feasible window lists from analyzing the polygonal map and applying pruning criteria. The pruning criteria consist of visibility analysis, heading analysis, and region-boundary constraints. Each goal-feasible window lists specifies an associated convex optimization problem, and the best of all locally-optimal paths through the goal-feasible window lists is the globally-optimal path. These ideas have been implemented in a computer program, with results showing considerably better performance than the exponential average-case behavior predicted.« less

The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

NASA Technical Reports Server (NTRS)

Plumlee, G. S.; Ridley, W. I.; Debraal, J. D.; Reed, M. H.

1993-01-01

Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

Investigation of progressive failure robustness and alternate load paths for damage tolerant structures

NASA Astrophysics Data System (ADS)

Marhadi, Kun Saptohartyadi

Structural optimization for damage tolerance under various unforeseen damage scenarios is computationally challenging. It couples non-linear progressive failure analysis with sampling-based stochastic analysis of random damage. The goal of this research was to understand the relationship between alternate load paths available in a structure and its damage tolerance, and to use this information to develop computationally efficient methods for designing damage tolerant structures. Progressive failure of a redundant truss structure subjected to small random variability was investigated to identify features that correlate with robustness and predictability of the structure's progressive failure. The identified features were used to develop numerical surrogate measures that permit computationally efficient deterministic optimization to achieve robustness and predictability of progressive failure. Analysis of damage tolerance on designs with robust progressive failure indicated that robustness and predictability of progressive failure do not guarantee damage tolerance. Damage tolerance requires a structure to redistribute its load to alternate load paths. In order to investigate the load distribution characteristics that lead to damage tolerance in structures, designs with varying degrees of damage tolerance were generated using brute force stochastic optimization. A method based on principal component analysis was used to describe load distributions (alternate load paths) in the structures. Results indicate that a structure that can develop alternate paths is not necessarily damage tolerant. The alternate load paths must have a required minimum load capability. Robustness analysis of damage tolerant optimum designs indicates that designs are tailored to specified damage. A design Optimized under one damage specification can be sensitive to other damages not considered. Effectiveness of existing load path definitions and characterizations were investigated for continuum structures. A load path definition using a relative compliance change measure (U* field) was demonstrated to be the most useful measure of load path. This measure provides quantitative information on load path trajectories and qualitative information on the effectiveness of the load path. The use of the U* description of load paths in optimizing structures for effective load paths was investigated.

Sensitivity analysis of an optimization-based trajectory planner for autonomous vehicles in urban environments

NASA Astrophysics Data System (ADS)

Hardy, Jason; Campbell, Mark; Miller, Isaac; Schimpf, Brian

2008-10-01

The local path planner implemented on Cornell's 2007 DARPA Urban Challenge entry vehicle Skynet utilizes a novel mixture of discrete and continuous path planning steps to facilitate a safe, smooth, and human-like driving behavior. The planner first solves for a feasible path through the local obstacle map using a grid based search algorithm. The resulting path is then refined using a cost-based nonlinear optimization routine with both hard and soft constraints. The behavior of this optimization is influenced by tunable weighting parameters which govern the relative cost contributions assigned to different path characteristics. This paper studies the sensitivity of the vehicle's performance to these path planner weighting parameters using a data driven simulation based on logged data from the National Qualifying Event. The performance of the path planner in both the National Qualifying Event and in the Urban Challenge is also presented and analyzed.

Towards the interaction between calcium carbide and water during gas-chromatographic determination of trace moisture in ultra-high purity ammonia.

PubMed

Trubyanov, Maxim M; Mochalov, Georgy M; Suvorov, Sergey S; Puzanov, Egor S; Petukhov, Anton N; Vorotyntsev, Ilya V; Vorotyntsev, Vladimir M

2018-07-27

The current study focuses on the processes involved during the flow conversion of water into acetylene in a calcium carbide reaction cell for the trace moisture analysis of ammonia by reaction gas chromatography. The factors negatively affecting the reproducibility and the accuracy of the measurements are suggested and discussed. The intramolecular reaction of the HOCaCCH intermediate was found to be a side reaction producing background acetylene during the contact of wet ammonia gas with calcium carbide. The presence of the HOCaCCH intermediate among the reaction products is confirmed by an FTIR spectral study of calcium carbide powder exposed to wet gas. The side reaction kinetics is evaluated experimentally and its influence on the results of the gas chromatographic measurements is discussed in relation to the determination of the optimal operating parameters for ammonia analysis. The reaction gas chromatography method for the trace moisture measurements in an ammonia matrix was experimentally compared to an FTIR long-path length gas cell technique to evaluate the accuracy limitations and the resource intensity. Copyright © 2018 Elsevier B.V. All rights reserved.

Associations between heat exposure, vigilance, and balance performance in summer tree fruit harvesters.

PubMed

Spector, June T; Krenz, Jennifer; Calkins, Miriam; Ryan, Dawn; Carmona, Jose; Pan, Mengjie; Zemke, Anna; Sampson, Paul D

2018-02-01

We sought to evaluate potential mediators of the relationship between heat exposure and traumatic injuries in outdoor agricultural workers. Linear mixed models were used to estimate associations between maximum work-shift Wet Bulb Globe Temperature (WBGT max ) and post-shift vigilance (reaction time) and postural sway (total path length) in a cross-sectional sample of 46 Washington State tree fruit harvesters in August-September 2015. The mean (SD) WBGT max was 27.4 (3.2)°C in August and 21.2 (2.0)°C in September. The mean pre-work-shift participant urine specific gravity indicated minimal dehydration. Twenty-four percent of participants exhibited possible excessive sleepiness. There was no association between WBGT max and post-shift reaction time or total path length. Heat exposure was not associated with impaired vigilance or balance in this study, in which the overall mean (SD) WBGT max was 25.9 (4.2)°C. However, the study identified opportunities to ensure adequate pre-work-shift hydration and to optimize sleep and work-shift timing in order to reduce occupational injury and heat-related illness risk. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sequential quadratic programming-based fast path planning algorithm subject to no-fly zone constraints

NASA Astrophysics Data System (ADS)

Liu, Wei; Ma, Shunjian; Sun, Mingwei; Yi, Haidong; Wang, Zenghui; Chen, Zengqiang

2016-08-01

Path planning plays an important role in aircraft guided systems. Multiple no-fly zones in the flight area make path planning a constrained nonlinear optimization problem. It is necessary to obtain a feasible optimal solution in real time. In this article, the flight path is specified to be composed of alternate line segments and circular arcs, in order to reformulate the problem into a static optimization one in terms of the waypoints. For the commonly used circular and polygonal no-fly zones, geometric conditions are established to determine whether or not the path intersects with them, and these can be readily programmed. Then, the original problem is transformed into a form that can be solved by the sequential quadratic programming method. The solution can be obtained quickly using the Sparse Nonlinear OPTimizer (SNOPT) package. Mathematical simulations are used to verify the effectiveness and rapidity of the proposed algorithm.

Time optimized path-choice in the termite hunting ant Megaponera analis.

PubMed

Frank, Erik T; Hönle, Philipp O; Linsenmair, K Eduard

2018-05-10

Trail network systems among ants have received a lot of scientific attention due to their various applications in problem solving of networks. Recent studies have shown that ants select the fastest available path when facing different velocities on different substrates, rather than the shortest distance. The progress of decision-making by these ants is determined by pheromone-based maintenance of paths, which is a collective decision. However, path optimization through individual decision-making remains mostly unexplored. Here we present the first study of time-optimized path selection via individual decision-making by scout ants. Megaponera analis scouts search for termite foraging sites and lead highly organized raid columns to them. The path of the scout determines the path of the column. Through installation of artificial roads around M. analis nests we were able to influence the pathway choice of the raids. After road installation 59% of all recorded raids took place completely or partly on the road, instead of the direct, i.e. distance-optimized, path through grass from the nest to the termites. The raid velocity on the road was more than double the grass velocity, the detour thus saved 34.77±23.01% of the travel time compared to a hypothetical direct path. The pathway choice of the ants was similar to a mathematical model of least time allowing us to hypothesize the underlying mechanisms regulating the behavior. Our results highlight the importance of individual decision-making in the foraging behavior of ants and show a new procedure of pathway optimization. © 2018. Published by The Company of Biologists Ltd.

Smell Detection Agent Based Optimization Algorithm

NASA Astrophysics Data System (ADS)

Vinod Chandra, S. S.

2016-09-01

In this paper, a novel nature-inspired optimization algorithm has been employed and the trained behaviour of dogs in detecting smell trails is adapted into computational agents for problem solving. The algorithm involves creation of a surface with smell trails and subsequent iteration of the agents in resolving a path. This algorithm can be applied in different computational constraints that incorporate path-based problems. Implementation of the algorithm can be treated as a shortest path problem for a variety of datasets. The simulated agents have been used to evolve the shortest path between two nodes in a graph. This algorithm is useful to solve NP-hard problems that are related to path discovery. This algorithm is also useful to solve many practical optimization problems. The extensive derivation of the algorithm can be enabled to solve shortest path problems.

Path synthesis of four-bar mechanisms using synergy of polynomial neural network and Stackelberg game theory

NASA Astrophysics Data System (ADS)

Ahmadi, Bahman; Nariman-zadeh, Nader; Jamali, Ali

2017-06-01

In this article, a novel approach based on game theory is presented for multi-objective optimal synthesis of four-bar mechanisms. The multi-objective optimization problem is modelled as a Stackelberg game. The more important objective function, tracking error, is considered as the leader, and the other objective function, deviation of the transmission angle from 90° (TA), is considered as the follower. In a new approach, a group method of data handling (GMDH)-type neural network is also utilized to construct an approximate model for the rational reaction set (RRS) of the follower. Using the proposed game-theoretic approach, the multi-objective optimal synthesis of a four-bar mechanism is then cast into a single-objective optimal synthesis using the leader variables and the obtained RRS of the follower. The superiority of using the synergy game-theoretic method of Stackelberg with a GMDH-type neural network is demonstrated for two case studies on the synthesis of four-bar mechanisms.

Reaction path of energetic materials using THOR code

NASA Astrophysics Data System (ADS)

Durães, L.; Campos, J.; Portugal, A.

1998-07-01

The method of predicting reaction path, using THOR code, allows for isobar and isochor adiabatic combustion and CJ detonation regimes, the calculation of the composition and thermodynamic properties of reaction products of energetic materials. THOR code assumes the thermodynamic equilibria of all possible products, for the minimum Gibbs free energy, using HL EoS. The code allows the possibility of estimating various sets of reaction products, obtained successively by the decomposition of the original reacting compound, as a function of the released energy. Two case studies of thermal decomposition procedure were selected, calculated and discussed—pure Ammonium Nitrate and its based explosive ANFO, and Nitromethane—because their equivalence ratio is respectively lower, near and greater than the stoicheiometry. Predictions of reaction path are in good correlation with experimental values, proving the validity of proposed method.

Codification of scan path parameters and development of perimeter scan strategies for 3D bowl-shaped laser forming

NASA Astrophysics Data System (ADS)

Tavakoli, A.; Naeini, H. Moslemi; Roohi, Amir H.; Gollo, M. Hoseinpour; Shahabad, Sh. Imani

2018-01-01

In the 3D laser forming process, developing an appropriate laser scan pattern for producing specimens with high quality and uniformity is critical. This study presents certain principles for developing scan paths. Seven scan path parameters are considered, including: (1) combined linear or curved path; (2) type of combined linear path; (3) order of scan sequences; (4) the position of the start point in each scan; (5) continuous or discontinuous scan path; (6) direction of scan path; and (7) angular arrangement of combined linear scan paths. Regarding these path parameters, ten combined linear scan patterns are presented. Numerical simulations show continuous hexagonal, scan pattern, scanning from outer to inner path, is the optimized. In addition, it is observed the position of the start point and the angular arrangement of scan paths is the most effective path parameters. Also, further experimentations show four sequences due to creat symmetric condition enhance the height of the bowl-shaped products and uniformity. Finally, the optimized hexagonal pattern was compared with the similar circular one. In the hexagonal scan path, distortion value and standard deviation rather to edge height of formed specimen is very low, and the edge height despite of decreasing length of scan path increases significantly compared to the circular scan path. As a result, four-sequence hexagonal scan pattern is proposed as the optimized perimeter scan path to produce bowl-shaped product.

Self-organization and solution of shortest-path optimization problems with memristive networks

NASA Astrophysics Data System (ADS)

Pershin, Yuriy V.; Di Ventra, Massimiliano

2013-07-01

We show that memristive networks, namely networks of resistors with memory, can efficiently solve shortest-path optimization problems. Indeed, the presence of memory (time nonlocality) promotes self organization of the network into the shortest possible path(s). We introduce a network entropy function to characterize the self-organized evolution, show the solution of the shortest-path problem and demonstrate the healing property of the solution path. Finally, we provide an algorithm to solve the traveling salesman problem. Similar considerations apply to networks of memcapacitors and meminductors, and networks with memory in various dimensions.

Computational study of the reactions of methanol with the hydroperoxyl and methyl radicals. 2. Accurate thermal rate constants.

PubMed

Alecu, I M; Truhlar, Donald G

2011-12-29

Multistructural canonical variational-transition-state theory with multidimensional tunneling (MS-CVT/MT) is employed to calculate thermal rate constants for the abstraction of hydrogen atoms from both positions of methanol by the hydroperoxyl and methyl radicals over the temperature range 100-3000 K. The M08-HX hybrid meta-generalized gradient approximation density functional and M08-HX with specific reaction parameters, both with the maug-cc-pVTZ basis set, were validated in part 1 of this study (Alecu, I. M.; Truhlar, D. G. J. Phys. Chem. A2011, 115, 2811) against highly accurate CCSDT(2)(Q)/CBS calculations for the energetics of these reactions, and they are used here to compute the properties of all stationary points and the energies, gradients, and Hessians of nonstationary points along each considered reaction path. The internal rotations in some of the transition states are found to be highly anharmonic and strongly coupled to each other, and they generate multiple structures (conformations) whose contributions are included in the partition function. It is shown that the previous estimates for these rate constants used to build kinetic models for the combustion of methanol, some of which were based on transition state theory calculations with one-dimensional tunneling corrections and harmonic-oscillator approximations or separable one-dimensional hindered rotor treatments of torsions, are appreciably different than the ones presently calculated using MS-CVT/MT. The rate constants obtained from the best MS-CVT/MT calculations carried out in this study, in which the important effects of corner cutting due to small and large reaction path curvature are captured via a microcanonical optimized multidimensional tunneling (μOMT) treatment, are recommended for future refinement of the kinetic model for methanol combustion. © 2011 American Chemical Society

Optimal Path Planning Program for Autonomous Speed Sprayer in Orchard Using Order-Picking Algorithm

NASA Astrophysics Data System (ADS)

Park, T. S.; Park, S. J.; Hwang, K. Y.; Cho, S. I.

This study was conducted to develop a software program which computes optimal path for autonomous navigation in orchard, especially for speed sprayer. Possibilities of autonomous navigation in orchard were shown by other researches which have minimized distance error between planned path and performed path. But, research of planning an optimal path for speed sprayer in orchard is hardly founded. In this study, a digital map and a database for orchard which contains GPS coordinate information (coordinates of trees and boundary of orchard) and entity information (heights and widths of trees, radius of main stem of trees, disease of trees) was designed. An orderpicking algorithm which has been used for management of warehouse was used to calculate optimum path based on the digital map. Database for digital map was created by using Microsoft Access and graphic interface for database was made by using Microsoft Visual C++ 6.0. It was possible to search and display information about boundary of an orchard, locations of trees, daily plan for scattering chemicals and plan optimal path on different orchard based on digital map, on each circumstance (starting speed sprayer in different location, scattering chemicals for only selected trees).

Path optimization with limited sensing ability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Sung Ha, E-mail: kang@math.gatech.edu; Kim, Seong Jun, E-mail: skim396@math.gatech.edu; Zhou, Haomin, E-mail: hmzhou@math.gatech.edu

2015-10-15

We propose a computational strategy to find the optimal path for a mobile sensor with limited coverage to traverse a cluttered region. The goal is to find one of the shortest feasible paths to achieve the complete scan of the environment. We pose the problem in the level set framework, and first consider a related question of placing multiple stationary sensors to obtain the full surveillance of the environment. By connecting the stationary locations using the nearest neighbor strategy, we form the initial guess for the path planning problem of the mobile sensor. Then the path is optimized by reducingmore » its length, via solving a system of ordinary differential equations (ODEs), while maintaining the complete scan of the environment. Furthermore, we use intermittent diffusion, which converts the ODEs into stochastic differential equations (SDEs), to find an optimal path whose length is globally minimal. To improve the computation efficiency, we introduce two techniques, one to remove redundant connecting points to reduce the dimension of the system, and the other to deal with the entangled path so the solution can escape the local traps. Numerical examples are shown to illustrate the effectiveness of the proposed method.« less

High-Resolution Free-Energy Landscape Analysis of α-Helical Protein Folding: HP35 and Its Double Mutant

PubMed Central

2013-01-01

The free-energy landscape can provide a quantitative description of folding dynamics, if determined as a function of an optimally chosen reaction coordinate. Here, we construct the optimal coordinate and the associated free-energy profile for all-helical proteins HP35 and its norleucine (Nle/Nle) double mutant, based on realistic equilibrium folding simulations [Piana et al. Proc. Natl. Acad. Sci. U.S.A.2012, 109, 17845]. From the obtained profiles, we directly determine such basic properties of folding dynamics as the configurations of the minima and transition states (TS), the formation of secondary structure and hydrophobic core during the folding process, the value of the pre-exponential factor and its relation to the transition path times, the relation between the autocorrelation times in TS and minima. We also present an investigation of the accuracy of the pre-exponential factor estimation based on the transition-path times. Four different estimations of the pre-exponential factor for both proteins give k0–1 values of approximately a few tens of nanoseconds. Our analysis gives detailed information about folding of the proteins and can serve as a rigorous common language for extensive comparison between experiment and simulation. PMID:24348206

High-Resolution Free-Energy Landscape Analysis of α-Helical Protein Folding: HP35 and Its Double Mutant.

PubMed

Banushkina, Polina V; Krivov, Sergei V

2013-12-10

The free-energy landscape can provide a quantitative description of folding dynamics, if determined as a function of an optimally chosen reaction coordinate. Here, we construct the optimal coordinate and the associated free-energy profile for all-helical proteins HP35 and its norleucine (Nle/Nle) double mutant, based on realistic equilibrium folding simulations [Piana et al. Proc. Natl. Acad. Sci. U.S.A. 2012 , 109 , 17845]. From the obtained profiles, we directly determine such basic properties of folding dynamics as the configurations of the minima and transition states (TS), the formation of secondary structure and hydrophobic core during the folding process, the value of the pre-exponential factor and its relation to the transition path times, the relation between the autocorrelation times in TS and minima. We also present an investigation of the accuracy of the pre-exponential factor estimation based on the transition-path times. Four different estimations of the pre-exponential factor for both proteins give k 0 -1 values of approximately a few tens of nanoseconds. Our analysis gives detailed information about folding of the proteins and can serve as a rigorous common language for extensive comparison between experiment and simulation.

An integrated experimental and theoretical reaction path search: analyses of the multistage reaction of an ionized diethylether dimer involving isomerization, proton transfer, and dissociation.

PubMed

Matsuda, Yoshiyuki; Xie, Min; Fujii, Asuka

2018-05-30

An ionization-induced multistage reaction of an ionized diethylether (DEE) dimer involving isomerization, proton transfer, and dissociation is investigated by combining infrared (IR) spectroscopy, tandem mass spectrometry, and a theoretical reaction path search. The vertically-ionized DEE dimer isomerizes to a hydrogen-bonded cluster of protonated DEE and the [DEE-H] radical through barrierless intermolecular proton transfer from the CH bond of the ionized moiety. This isomerization process is confirmed by IR spectroscopy and the theoretical reaction path search. The multiple dissociation pathways following the isomerization are analyzed by tandem mass spectrometry. The isomerized cluster dissociates stepwise into a [protonated DEE-acetaldehyde (AA)] cluster, protonated DEE, and protonated AA. The structure of the fragment ion is also analyzed by IR spectroscopy. The reaction map of the multistage processes is revealed through a harmony of these experimental and theoretical methods.

Quad-rotor flight path energy optimization

NASA Astrophysics Data System (ADS)

Kemper, Edward

Quad-Rotor unmanned areal vehicles (UAVs) have been a popular area of research and development in the last decade, especially with the advent of affordable microcontrollers like the MSP 430 and the Raspberry Pi. Path-Energy Optimization is an area that is well developed for linear systems. In this thesis, this idea of path-energy optimization is extended to the nonlinear model of the Quad-rotor UAV. The classical optimization technique is adapted to the nonlinear model that is derived for the problem at hand, coming up with a set of partial differential equations and boundary value conditions to solve these equations. Then, different techniques to implement energy optimization algorithms are tested using simulations in Python. First, a purely nonlinear approach is used. This method is shown to be computationally intensive, with no practical solution available in a reasonable amount of time. Second, heuristic techniques to minimize the energy of the flight path are tested, using Ziegler-Nichols' proportional integral derivative (PID) controller tuning technique. Finally, a brute force look-up table based PID controller is used. Simulation results of the heuristic method show that both reliable control of the system and path-energy optimization are achieved in a reasonable amount of time.

The MATCHIT Automaton: Exploiting Compartmentalization for the Synthesis of Branched Polymers

PubMed Central

Weyland, Mathias S.; Fellermann, Harold; Hadorn, Maik; Sorek, Daniel; Lancet, Doron; Rasmussen, Steen; Füchslin, Rudolf M.

2013-01-01

We propose an automaton, a theoretical framework that demonstrates how to improve the yield of the synthesis of branched chemical polymer reactions. This is achieved by separating substeps of the path of synthesis into compartments. We use chemical containers (chemtainers) to carry the substances through a sequence of fixed successive compartments. We describe the automaton in mathematical terms and show how it can be configured automatically in order to synthesize a given branched polymer target. The algorithm we present finds an optimal path of synthesis in linear time. We discuss how the automaton models compartmentalized structures found in cells, such as the endoplasmic reticulum and the Golgi apparatus, and we show how this compartmentalization can be exploited for the synthesis of branched polymers such as oligosaccharides. Lastly, we show examples of artificial branched polymers and discuss how the automaton can be configured to synthesize them with maximal yield. PMID:24489601

Seamount Hydrothermal Systems as Analogies for Ocean Worlds: Reaction Paths Throughout the Lo'ihi Seamount (Hawaii Archipelago)

NASA Astrophysics Data System (ADS)

Milesi, V.; Shock, E.

2018-05-01

Thermodynamic modeling is performed to investigate the possible reaction paths of sea water throughout the Lo'ihi seamount and the associated geochemical supplies of energy that can support autotrophic microbial communities.

Differential-Evolution Control Parameter Optimization for Unmanned Aerial Vehicle Path Planning

PubMed Central

Kok, Kai Yit; Rajendran, Parvathy

2016-01-01

The differential evolution algorithm has been widely applied on unmanned aerial vehicle (UAV) path planning. At present, four random tuning parameters exist for differential evolution algorithm, namely, population size, differential weight, crossover, and generation number. These tuning parameters are required, together with user setting on path and computational cost weightage. However, the optimum settings of these tuning parameters vary according to application. Instead of trial and error, this paper presents an optimization method of differential evolution algorithm for tuning the parameters of UAV path planning. The parameters that this research focuses on are population size, differential weight, crossover, and generation number. The developed algorithm enables the user to simply define the weightage desired between the path and computational cost to converge with the minimum generation required based on user requirement. In conclusion, the proposed optimization of tuning parameters in differential evolution algorithm for UAV path planning expedites and improves the final output path and computational cost. PMID:26943630

Review of computer simulations of isotope effects on biochemical reactions: From the Bigeleisen equation to Feynman's path integral.

PubMed

Wong, Kin-Yiu; Xu, Yuqing; Xu, Liang

2015-11-01

Enzymatic reactions are integral components in many biological functions and malfunctions. The iconic structure of each reaction path for elucidating the reaction mechanism in details is the molecular structure of the rate-limiting transition state (RLTS). But RLTS is very hard to get caught or to get visualized by experimentalists. In spite of the lack of explicit molecular structure of the RLTS in experiment, we still can trace out the RLTS unique "fingerprints" by measuring the isotope effects on the reaction rate. This set of "fingerprints" is considered as a most direct probe of RLTS. By contrast, for computer simulations, oftentimes molecular structures of a number of TS can be precisely visualized on computer screen, however, theoreticians are not sure which TS is the actual rate-limiting one. As a result, this is an excellent stage setting for a perfect "marriage" between experiment and theory for determining the structure of RLTS, along with the reaction mechanism, i.e., experimentalists are responsible for "fingerprinting", whereas theoreticians are responsible for providing candidates that match the "fingerprints". In this Review, the origin of isotope effects on a chemical reaction is discussed from the perspectives of classical and quantum worlds, respectively (e.g., the origins of the inverse kinetic isotope effects and all the equilibrium isotope effects are purely from quantum). The conventional Bigeleisen equation for isotope effect calculations, as well as its refined version in the framework of Feynman's path integral and Kleinert's variational perturbation (KP) theory for systematically incorporating anharmonicity and (non-parabolic) quantum tunneling, are also presented. In addition, the outstanding interplay between theory and experiment for successfully deducing the RLTS structures and the reaction mechanisms is demonstrated by applications on biochemical reactions, namely models of bacterial squalene-to-hopene polycyclization and RNA 2'-O-transphosphorylation. For all these applications, we used our recently-developed path-integral method based on the KP theory, called automated integration-free path-integral (AIF-PI) method, to perform ab initio path-integral calculations of isotope effects. As opposed to the conventional path-integral molecular dynamics (PIMD) and Monte Carlo (PIMC) simulations, values calculated from our AIF-PI path-integral method can be as precise as (not as accurate as) the numerical precision of the computing machine. Lastly, comments are made on the general challenges in theoretical modeling of candidates matching the experimental "fingerprints" of RLTS. This article is part of a Special Issue entitled: Enzyme Transition States from Theory and Experiment. Copyright © 2015 Elsevier B.V. All rights reserved.

Teleconnection Paths via Climate Network Direct Link Detection.

PubMed

Zhou, Dong; Gozolchiani, Avi; Ashkenazy, Yosef; Havlin, Shlomo

2015-12-31

Teleconnections describe remote connections (typically thousands of kilometers) of the climate system. These are of great importance in climate dynamics as they reflect the transportation of energy and climate change on global scales (like the El Niño phenomenon). Yet, the path of influence propagation between such remote regions, and weighting associated with different paths, are only partially known. Here we propose a systematic climate network approach to find and quantify the optimal paths between remotely distant interacting locations. Specifically, we separate the correlations between two grid points into direct and indirect components, where the optimal path is found based on a minimal total cost function of the direct links. We demonstrate our method using near surface air temperature reanalysis data, on identifying cross-latitude teleconnections and their corresponding optimal paths. The proposed method may be used to quantify and improve our understanding regarding the emergence of climate patterns on global scales.

Dynamic path planning for mobile robot based on particle swarm optimization

NASA Astrophysics Data System (ADS)

Wang, Yong; Cai, Feng; Wang, Ying

2017-08-01

In the contemporary, robots are used in many fields, such as cleaning, medical treatment, space exploration, disaster relief and so on. The dynamic path planning of robot without collision is becoming more and more the focus of people's attention. A new method of path planning is proposed in this paper. Firstly, the motion space model of the robot is established by using the MAKLINK graph method. Then the A* algorithm is used to get the shortest path from the start point to the end point. Secondly, this paper proposes an effective method to detect and avoid obstacles. When an obstacle is detected on the shortest path, the robot will choose the nearest safety point to move. Moreover, calculate the next point which is nearest to the target. Finally, the particle swarm optimization algorithm is used to optimize the path. The experimental results can prove that the proposed method is more effective.

CMPF: class-switching minimized pathfinding in metabolic networks.

PubMed

Lim, Kevin; Wong, Limsoon

2012-01-01

The metabolic network is an aggregation of enzyme catalyzed reactions that converts one compound to another. Paths in a metabolic network are a sequence of enzymes that describe how a chemical compound of interest can be produced in a biological system. As the number of such paths is quite large, many methods have been developed to score paths so that the k-shortest paths represent the set of paths that are biologically meaningful or efficient. However, these approaches do not consider whether the sequence of enzymes can be manufactured in the same pathway/species/localization. As a result, a predicted sequence might consist of groups of enzymes that operate in distinct pathway/species/localization and may not truly reflect the events occurring within cell. We propose a path weighting method CMPF (Class-switching Minimized Pathfinder) to search for routes in a metabolic network which minimizes pathway switching. In biological terms, a pathway is a series of chemical reactions which define a specific function (e.g. glycolysis). We conjecture that routes that cross many pathways are inefficient since different pathways define different metabolic functions. In addition, native routes are also well characterized within pathways, suggesting that reasonable paths should not involve too many pathway switches. Our method can be generalized when reactions participate in a class set (e.g., pathways, species or cellular localization) so that the paths predicted have minimal class crossings. We show that our method generates k-paths that involve the least number of class switching. In addition, we also show that native paths are recoverable and alternative paths deviates less from native paths compared to other methods. This suggests that paths ranked by our method could be a way to predict paths that are likely to occur in biological systems.

Electronic Structure Theory Study of the Microsolvated F(-)(H2O) + CH3I SN2 Reaction.

PubMed

Zhang, Jiaxu; Yang, Li; Sheng, Li

2016-05-26

The potential energy profile of microhydrated fluorine ion reaction with methyl iodine has been characterized by extensive electronic structure calculations. Both hydrogen-bonded F(-)(H2O)---HCH2I and ion-dipole F(-)(H2O)---CH3I complexes are formed for the reaction entrance and the PES in vicinity of these complexes is very flat, which may have important implications for the reaction dynamics. The water molecule remains on the fluorine side until the reactive system goes to the SN2 saddle point. It can easily move to the iodine side with little barrier, but in a nonsynchronous reaction path after the dynamical bottleneck to the reaction, which supports the previous prediction for microsolvated SN2 systems. The influence of solvating water molecule on the reaction mechanism is probed by comparing with the influence of the nonsolvated analogue and other microsolvated SN2 systems. Taking the CCSD(T) single-point calculations based on MP2-optimized geometries as benchmark, the DFT functionals B97-1 and B3LYP are found to better characterize the potential energy profile for the title reaction and are recommended as the preferred methods for the direct dynamics simulations to uncover the dynamic behaviors.

Path optimization method for the sign problem

NASA Astrophysics Data System (ADS)

Ohnishi, Akira; Mori, Yuto; Kashiwa, Kouji

2018-03-01

We propose a path optimization method (POM) to evade the sign problem in the Monte-Carlo calculations for complex actions. Among many approaches to the sign problem, the Lefschetz-thimble path-integral method and the complex Langevin method are promising and extensively discussed. In these methods, real field variables are complexified and the integration manifold is determined by the flow equations or stochastically sampled. When we have singular points of the action or multiple critical points near the original integral surface, however, we have a risk to encounter the residual and global sign problems or the singular drift term problem. One of the ways to avoid the singular points is to optimize the integration path which is designed not to hit the singular points of the Boltzmann weight. By specifying the one-dimensional integration-path as z = t +if(t)(f ɛ R) and by optimizing f(t) to enhance the average phase factor, we demonstrate that we can avoid the sign problem in a one-variable toy model for which the complex Langevin method is found to fail. In this proceedings, we propose POM and discuss how we can avoid the sign problem in a toy model. We also discuss the possibility to utilize the neural network to optimize the path.

Capture reactions on C-14 in nonstandard big bang nucleosynthesis

NASA Technical Reports Server (NTRS)

Wiescher, Michael; Gorres, Joachim; Thielemann, Friedrich-Karl

1990-01-01

Nonstandard big bang nucleosynthesis leads to the production of C-14. The further reaction path depends on the depletion of C-14 by either photon, alpha, or neutron capture reactions. The nucleus C-14 is of particular importance in these scenarios because it forms a bottleneck for the production of heavier nuclei A greater than 14. The reaction rates of all three capture reactions at big bang conditions are discussed, and it is shown that the resulting reaction path, leading to the production of heavier elements, is dominated by the (p, gamma) and (n, gamma) rates, contrary to earlier suggestions.

Design of Quiet Rotorcraft Approach Trajectories

NASA Technical Reports Server (NTRS)

Padula, Sharon L.; Burley, Casey L.; Boyd, D. Douglas, Jr.; Marcolini, Michael A.

2009-01-01

A optimization procedure for identifying quiet rotorcraft approach trajectories is proposed and demonstrated. The procedure employs a multi-objective genetic algorithm in order to reduce noise and create approach paths that will be acceptable to pilots and passengers. The concept is demonstrated by application to two different helicopters. The optimized paths are compared with one another and to a standard 6-deg approach path. The two demonstration cases validate the optimization procedure but highlight the need for improved noise prediction techniques and for additional rotorcraft acoustic data sets.

Converging Towards the Optimal Path to Extinction

DTIC Science & Technology

2011-01-01

the reproductive rate R0 should be greater than but very close to 1. However, most real diseases have R0 larger than 1.5, which translates into a...can analytically find an expression for the action along the optimal path. The expression for the action is a function of k and the reproductive number...the optimal path for a range of values of the reproductive number R0. In contrast to the prior two examples, here the action must be computed

Multi-path variational transition state theory for chemical reaction rates of complex polyatomic species: ethanol + OH reactions.

PubMed

Zheng, Jingjing; Truhlar, Donald G

2012-01-01

Complex molecules often have many structures (conformations) of the reactants and the transition states, and these structures may be connected by coupled-mode torsions and pseudorotations; some but not all structures may have hydrogen bonds in the transition state or reagents. A quantitative theory of the reaction rates of complex molecules must take account of these structures, their coupled-mode nature, their qualitatively different character, and the possibility of merging reaction paths at high temperature. We have recently developed a coupled-mode theory called multi-structural variational transition state theory (MS-VTST) and an extension, called multi-path variational transition state theory (MP-VTST), that includes a treatment of the differences in the multi-dimensional tunneling paths and their contributions to the reaction rate. The MP-VTST method was presented for unimolecular reactions in the original paper and has now been extended to bimolecular reactions. The MS-VTST and MP-VTST formulations of variational transition state theory include multi-faceted configuration-space dividing surfaces to define the variational transition state. They occupy an intermediate position between single-conformation variational transition state theory (VTST), which has been used successfully for small molecules, and ensemble-averaged variational transition state theory (EA-VTST), which has been used successfully for enzyme kinetics. The theories are illustrated and compared here by application to three thermal rate constants for reactions of ethanol with hydroxyl radical--reactions with 4, 6, and 14 saddle points.

Robust Flight Path Determination for Mars Precision Landing Using Genetic Algorithms

NASA Technical Reports Server (NTRS)

Bayard, David S.; Kohen, Hamid

1997-01-01

This paper documents the application of genetic algorithms (GAs) to the problem of robust flight path determination for Mars precision landing. The robust flight path problem is defined here as the determination of the flight path which delivers a low-lift open-loop controlled vehicle to its desired final landing location while minimizing the effect of perturbations due to uncertainty in the atmospheric model and entry conditions. The genetic algorithm was capable of finding solutions which reduced the landing error from 111 km RMS radial (open-loop optimal) to 43 km RMS radial (optimized with respect to perturbations) using 200 hours of computation on an Ultra-SPARC workstation. Further reduction in the landing error is possible by going to closed-loop control which can utilize the GA optimized paths as nominal trajectories for linearization.

Generalized Ensemble Sampling of Enzyme Reaction Free Energy Pathways

PubMed Central

Wu, Dongsheng; Fajer, Mikolai I.; Cao, Liaoran; Cheng, Xiaolin; Yang, Wei

2016-01-01

Free energy path sampling plays an essential role in computational understanding of chemical reactions, particularly those occurring in enzymatic environments. Among a variety of molecular dynamics simulation approaches, the generalized ensemble sampling strategy is uniquely attractive for the fact that it not only can enhance the sampling of rare chemical events but also can naturally ensure consistent exploration of environmental degrees of freedom. In this review, we plan to provide a tutorial-like tour on an emerging topic: generalized ensemble sampling of enzyme reaction free energy path. The discussion is largely focused on our own studies, particularly ones based on the metadynamics free energy sampling method and the on-the-path random walk path sampling method. We hope that this mini presentation will provide interested practitioners some meaningful guidance for future algorithm formulation and application study. PMID:27498634

In Search of the Optimal Path: How Learners at Task Use an Online Dictionary

ERIC Educational Resources Information Center

Hamel, Marie-Josee

2012-01-01

We have analyzed circa 180 navigation paths followed by six learners while they performed three language encoding tasks at the computer using an online dictionary prototype. Our hypothesis was that learners who follow an "optimal path" while navigating within the dictionary, using its search and look-up functions, would have a high chance of…

A systematic FPGA acceleration design for applications based on convolutional neural networks

NASA Astrophysics Data System (ADS)

Dong, Hao; Jiang, Li; Li, Tianjian; Liang, Xiaoyao

2018-04-01

Most FPGA accelerators for convolutional neural network are designed to optimize the inner acceleration and are ignored of the optimization for the data path between the inner accelerator and the outer system. This could lead to poor performance in applications like real time video object detection. We propose a brand new systematic FPFA acceleration design to solve this problem. This design takes the data path optimization between the inner accelerator and the outer system into consideration and optimizes the data path using techniques like hardware format transformation, frame compression. It also takes fixed-point, new pipeline technique to optimize the inner accelerator. All these make the final system's performance very good, reaching about 10 times the performance comparing with the original system.

Quantum Monte Carlo tunneling from quantum chemistry to quantum annealing

NASA Astrophysics Data System (ADS)

Mazzola, Guglielmo; Smelyanskiy, Vadim N.; Troyer, Matthias

2017-10-01

Quantum tunneling is ubiquitous across different fields, from quantum chemical reactions and magnetic materials to quantum simulators and quantum computers. While simulating the real-time quantum dynamics of tunneling is infeasible for high-dimensional systems, quantum tunneling also shows up in quantum Monte Carlo (QMC) simulations, which aim to simulate quantum statistics with resources growing only polynomially with the system size. Here we extend the recent results obtained for quantum spin models [Phys. Rev. Lett. 117, 180402 (2016), 10.1103/PhysRevLett.117.180402], and we study continuous-variable models for proton transfer reactions. We demonstrate that QMC simulations efficiently recover the scaling of ground-state tunneling rates due to the existence of an instanton path, which always connects the reactant state with the product. We discuss the implications of our results in the context of quantum chemical reactions and quantum annealing, where quantum tunneling is expected to be a valuable resource for solving combinatorial optimization problems.

Dynamic path planning for autonomous driving on various roads with avoidance of static and moving obstacles

NASA Astrophysics Data System (ADS)

Hu, Xuemin; Chen, Long; Tang, Bo; Cao, Dongpu; He, Haibo

2018-02-01

This paper presents a real-time dynamic path planning method for autonomous driving that avoids both static and moving obstacles. The proposed path planning method determines not only an optimal path, but also the appropriate acceleration and speed for a vehicle. In this method, we first construct a center line from a set of predefined waypoints, which are usually obtained from a lane-level map. A series of path candidates are generated by the arc length and offset to the center line in the s - ρ coordinate system. Then, all of these candidates are converted into Cartesian coordinates. The optimal path is selected considering the total cost of static safety, comfortability, and dynamic safety; meanwhile, the appropriate acceleration and speed for the optimal path are also identified. Various types of roads, including single-lane roads and multi-lane roads with static and moving obstacles, are designed to test the proposed method. The simulation results demonstrate the effectiveness of the proposed method, and indicate its wide practical application to autonomous driving.

Research on global path planning based on ant colony optimization for AUV

NASA Astrophysics Data System (ADS)

Wang, Hong-Jian; Xiong, Wei

2009-03-01

Path planning is an important issue for autonomous underwater vehicles (AUVs) traversing an unknown environment such as a sea floor, a jungle, or the outer celestial planets. For this paper, global path planning using large-scale chart data was studied, and the principles of ant colony optimization (ACO) were applied. This paper introduced the idea of a visibility graph based on the grid workspace model. It also brought a series of pheromone updating rules for the ACO planning algorithm. The operational steps of the ACO algorithm are proposed as a model for a global path planning method for AUV. To mimic the process of smoothing a planned path, a cutting operator and an insertion-point operator were designed. Simulation results demonstrated that the ACO algorithm is suitable for global path planning. The system has many advantages, including that the operating path of the AUV can be quickly optimized, and it is shorter, safer, and smoother. The prototype system successfully demonstrated the feasibility of the concept, proving it can be applied to surveys of unstructured unmanned environments.

UAV path planning using artificial potential field method updated by optimal control theory

NASA Astrophysics Data System (ADS)

Chen, Yong-bo; Luo, Guan-chen; Mei, Yue-song; Yu, Jian-qiao; Su, Xiao-long

2016-04-01

The unmanned aerial vehicle (UAV) path planning problem is an important assignment in the UAV mission planning. Based on the artificial potential field (APF) UAV path planning method, it is reconstructed into the constrained optimisation problem by introducing an additional control force. The constrained optimisation problem is translated into the unconstrained optimisation problem with the help of slack variables in this paper. The functional optimisation method is applied to reform this problem into an optimal control problem. The whole transformation process is deduced in detail, based on a discrete UAV dynamic model. Then, the path planning problem is solved with the help of the optimal control method. The path following process based on the six degrees of freedom simulation model of the quadrotor helicopters is introduced to verify the practicability of this method. Finally, the simulation results show that the improved method is more effective in planning path. In the planning space, the length of the calculated path is shorter and smoother than that using traditional APF method. In addition, the improved method can solve the dead point problem effectively.

A Comparison of Risk Sensitive Path Planning Methods for Aircraft Emergency Landing

NASA Technical Reports Server (NTRS)

Meuleau, Nicolas; Plaunt, Christian; Smith, David E.; Smith, Tristan

2009-01-01

Determining the best site to land a damaged aircraft presents some interesting challenges for standard path planning techniques. There are multiple possible locations to consider, the space is 3-dimensional with dynamics, the criteria for a good path is determined by overall risk rather than distance or time, and optimization really matters, since an improved path corresponds to greater expected survival rate. We have investigated a number of different path planning methods for solving this problem, including cell decomposition, visibility graphs, probabilistic road maps (PRMs), and local search techniques. In their pure form, none of these techniques have proven to be entirely satisfactory - some are too slow or unpredictable, some produce highly non-optimal paths or do not find certain types of paths, and some do not cope well with the dynamic constraints when controllability is limited. In the end, we are converging towards a hybrid technique that involves seeding a roadmap with a layered visibility graph, using PRM to extend that roadmap, and using local search to further optimize the resulting paths. We describe the techniques we have investigated, report on our experiments with these techniques, and discuss when and why various techniques were unsatisfactory.

Theoretical investigation on the mechanism and dynamics of oxo exchange of neptunyl(VI) hydroxide in aqueous solution.

PubMed

Yang, Xia; Chai, Zhifang; Wang, Dongqi

2015-03-21

Four types of reaction mechanisms for the oxo ligand exchange of monomeric and dimeric neptunyl(VI) hydroxide in aqueous solution were explored computationally using density functional theory (DFT) and ab initio classical molecular dynamics. The obtained results were compared with previous studies on the oxo exchange of uranyl hydroxide, as well as with experiments. It is found that the stable T-shaped [NpO3(OH)3](3-) intermediate is a key species for oxo exchange in the proton transfer in mononuclear Path I and binuclear Path IV, similar to the case of uranyl(VI) hydroxide. Path I is thought to be the preferred oxo exchange mechanism for neptunyl(VI) hydroxide in our calculations, due to the lower activation energy (22.7 and 13.1 kcal mol(-1) for ΔG(‡) and ΔH(‡), respectively) of the overall reaction. Path II via a cis-neptunyl structure assisted by a water molecule might be a competitive channel against Path I with a mononuclear mechanism, owing to a rapid dynamical process occurring in Path II. In Path IV with the binuclear mechanism, oxo exchange is accomplished via the interaction between [NpO2(OH)4](2-) and T-shaped [NpO3(OH)3](3-) with a low activation energy for the rate-determining step, however, the overall energy required to fulfill the reaction is slightly higher than that in mononuclear Path I, suggesting a possible binuclear process in the higher energy region. The chemical bonding evolution along the reaction pathways was discussed by using topological methodologies of the electron localization function (ELF).

Optimal Paths in Gliding Flight

NASA Astrophysics Data System (ADS)

Wolek, Artur

Underwater gliders are robust and long endurance ocean sampling platforms that are increasingly being deployed in coastal regions. This new environment is characterized by shallow waters and significant currents that can challenge the mobility of these efficient (but traditionally slow moving) vehicles. This dissertation aims to improve the performance of shallow water underwater gliders through path planning. The path planning problem is formulated for a dynamic particle (or "kinematic car") model. The objective is to identify the path which satisfies specified boundary conditions and minimizes a particular cost. Several cost functions are considered. The problem is addressed using optimal control theory. The length scales of interest for path planning are within a few turn radii. First, an approach is developed for planning minimum-time paths, for a fixed speed glider, that are sub-optimal but are guaranteed to be feasible in the presence of unknown time-varying currents. Next the minimum-time problem for a glider with speed controls, that may vary between the stall speed and the maximum speed, is solved. Last, optimal paths that minimize change in depth (equivalently, maximize range) are investigated. Recognizing that path planning alone cannot overcome all of the challenges associated with significant currents and shallow waters, the design of a novel underwater glider with improved capabilities is explored. A glider with a pneumatic buoyancy engine (allowing large, rapid buoyancy changes) and a cylindrical moving mass mechanism (generating large pitch and roll moments) is designed, manufactured, and tested to demonstrate potential improvements in speed and maneuverability.

The Study of Intelligent Vehicle Navigation Path Based on Behavior Coordination of Particle Swarm.

PubMed

Han, Gaining; Fu, Weiping; Wang, Wen

2016-01-01

In the behavior dynamics model, behavior competition leads to the shock problem of the intelligent vehicle navigation path, because of the simultaneous occurrence of the time-variant target behavior and obstacle avoidance behavior. Considering the safety and real-time of intelligent vehicle, the particle swarm optimization (PSO) algorithm is proposed to solve these problems for the optimization of weight coefficients of the heading angle and the path velocity. Firstly, according to the behavior dynamics model, the fitness function is defined concerning the intelligent vehicle driving characteristics, the distance between intelligent vehicle and obstacle, and distance of intelligent vehicle and target. Secondly, behavior coordination parameters that minimize the fitness function are obtained by particle swarm optimization algorithms. Finally, the simulation results show that the optimization method and its fitness function can improve the perturbations of the vehicle planning path and real-time and reliability.

The Study of Intelligent Vehicle Navigation Path Based on Behavior Coordination of Particle Swarm

PubMed Central

Han, Gaining; Fu, Weiping; Wang, Wen

2016-01-01

In the behavior dynamics model, behavior competition leads to the shock problem of the intelligent vehicle navigation path, because of the simultaneous occurrence of the time-variant target behavior and obstacle avoidance behavior. Considering the safety and real-time of intelligent vehicle, the particle swarm optimization (PSO) algorithm is proposed to solve these problems for the optimization of weight coefficients of the heading angle and the path velocity. Firstly, according to the behavior dynamics model, the fitness function is defined concerning the intelligent vehicle driving characteristics, the distance between intelligent vehicle and obstacle, and distance of intelligent vehicle and target. Secondly, behavior coordination parameters that minimize the fitness function are obtained by particle swarm optimization algorithms. Finally, the simulation results show that the optimization method and its fitness function can improve the perturbations of the vehicle planning path and real-time and reliability. PMID:26880881

Calibration of neural networks using genetic algorithms, with application to optimal path planning

NASA Technical Reports Server (NTRS)

Smith, Terence R.; Pitney, Gilbert A.; Greenwood, Daniel

1987-01-01

Genetic algorithms (GA) are used to search the synaptic weight space of artificial neural systems (ANS) for weight vectors that optimize some network performance function. GAs do not suffer from some of the architectural constraints involved with other techniques and it is straightforward to incorporate terms into the performance function concerning the metastructure of the ANS. Hence GAs offer a remarkably general approach to calibrating ANS. GAs are applied to the problem of calibrating an ANS that finds optimal paths over a given surface. This problem involves training an ANS on a relatively small set of paths and then examining whether the calibrated ANS is able to find good paths between arbitrary start and end points on the surface.

Stochastic Evolutionary Algorithms for Planning Robot Paths

NASA Technical Reports Server (NTRS)

Fink, Wolfgang; Aghazarian, Hrand; Huntsberger, Terrance; Terrile, Richard

2006-01-01

A computer program implements stochastic evolutionary algorithms for planning and optimizing collision-free paths for robots and their jointed limbs. Stochastic evolutionary algorithms can be made to produce acceptably close approximations to exact, optimal solutions for path-planning problems while often demanding much less computation than do exhaustive-search and deterministic inverse-kinematics algorithms that have been used previously for this purpose. Hence, the present software is better suited for application aboard robots having limited computing capabilities (see figure). The stochastic aspect lies in the use of simulated annealing to (1) prevent trapping of an optimization algorithm in local minima of an energy-like error measure by which the fitness of a trial solution is evaluated while (2) ensuring that the entire multidimensional configuration and parameter space of the path-planning problem is sampled efficiently with respect to both robot joint angles and computation time. Simulated annealing is an established technique for avoiding local minima in multidimensional optimization problems, but has not, until now, been applied to planning collision-free robot paths by use of low-power computers.

Path Planning Method in Multi-obstacle Marine Environment

NASA Astrophysics Data System (ADS)

Zhang, Jinpeng; Sun, Hanxv

2017-12-01

In this paper, an improved algorithm for particle swarm optimization is proposed for the application of underwater robot in the complex marine environment. Not only did consider to avoid obstacles when path planning, but also considered the current direction and the size effect on the performance of the robot dynamics. The algorithm uses the trunk binary tree structure to construct the path search space and A * heuristic search method is used in the search space to find a evaluation standard path. Then the particle swarm algorithm to optimize the path by adjusting evaluation function, which makes the underwater robot in the current navigation easier to control, and consume less energy.

Real-time Collision Avoidance and Path Optimizer for Semi-autonomous UAVs.

NASA Astrophysics Data System (ADS)

Hawary, A. F.; Razak, N. A.

2018-05-01

Whilst UAV offers a potentially cheaper and more localized observation platform than current satellite or land-based approaches, it requires an advance path planner to reveal its true potential, particularly in real-time missions. Manual control by human will have limited line-of-sights and prone to errors due to careless and fatigue. A good alternative solution is to equip the UAV with semi-autonomous capabilities that able to navigate via a pre-planned route in real-time fashion. In this paper, we propose an easy-and-practical path optimizer based on the classical Travelling Salesman Problem and adopts a brute force search method to re-optimize the route in the event of collisions using range finder sensor. The former utilizes a Simple Genetic Algorithm and the latter uses Nearest Neighbour algorithm. Both algorithms are combined to optimize the route and avoid collision at once. Although many researchers proposed various path planning algorithms, we find that it is difficult to integrate on a basic UAV model and often lacks of real-time collision detection optimizer. Therefore, we explore a practical benefit from this approach using on-board Arduino and Ardupilot controllers by manually emulating the motion of an actual UAV model prior to test on the flying site. The result showed that the range finder sensor provides a real-time data to the algorithm to find a collision-free path and eventually optimized the route successfully.

Application of the nudged elastic band method to the point-to-point radio wave ray tracing in IRI modeled ionosphere

NASA Astrophysics Data System (ADS)

Nosikov, I. A.; Klimenko, M. V.; Bessarab, P. F.; Zhbankov, G. A.

2017-07-01

Point-to-point ray tracing is an important problem in many fields of science. While direct variational methods where some trajectory is transformed to an optimal one are routinely used in calculations of pathways of seismic waves, chemical reactions, diffusion processes, etc., this approach is not widely known in ionospheric point-to-point ray tracing. We apply the Nudged Elastic Band (NEB) method to a radio wave propagation problem. In the NEB method, a chain of points which gives a discrete representation of the radio wave ray is adjusted iteratively to an optimal configuration satisfying the Fermat's principle, while the endpoints of the trajectory are kept fixed according to the boundary conditions. Transverse displacements define the radio ray trajectory, while springs between the points control their distribution along the ray. The method is applied to a study of point-to-point ionospheric ray tracing, where the propagation medium is obtained with the International Reference Ionosphere model taking into account traveling ionospheric disturbances. A 2-dimensional representation of the optical path functional is developed and used to gain insight into the fundamental difference between high and low rays. We conclude that high and low rays are minima and saddle points of the optical path functional, respectively.

Method of interplanetary trajectory optimization for the spacecraft with low thrust and swing-bys

NASA Astrophysics Data System (ADS)

Konstantinov, M. S.; Thein, M.

2017-07-01

The method developed to avoid the complexity of solving the multipoint boundary value problem while optimizing interplanetary trajectories of the spacecraft with electric propulsion and a sequence of swing-bys is presented in the paper. This method is based on the use of the preliminary problem solutions for the impulsive trajectories. The preliminary problem analyzed at the first stage of the study is formulated so that the analysis and optimization of a particular flight path is considered as the unconstrained minimum in the space of the selectable parameters. The existing methods can effectively solve this problem and make it possible to identify rational flight paths (the sequence of swing-bys) to receive the initial approximation for the main characteristics of the flight path (dates, values of the hyperbolic excess velocity, etc.). These characteristics can be used to optimize the trajectory of the spacecraft with electric propulsion. The special feature of the work is the introduction of the second (intermediate) stage of the research. At this stage some characteristics of the analyzed flight path (e.g. dates of swing-bys) are fixed and the problem is formulated so that the trajectory of the spacecraft with electric propulsion is optimized on selected sites of the flight path. The end-to-end optimization is carried out at the third (final) stage of the research. The distinctive feature of this stage is the analysis of the full set of optimal conditions for the considered flight path. The analysis of the characteristics of the optimal flight trajectories to Jupiter with Earth, Venus and Mars swing-bys for the spacecraft with electric propulsion are presented. The paper shows that the spacecraft weighing more than 7150 kg can be delivered into the vicinity of Jupiter along the trajectory with two Earth swing-bys by use of the space transportation system based on the "Angara A5" rocket launcher, the chemical upper stage "KVTK" and the electric propulsion system with input electrical power of 100 kW.

Optimization of magnet end-winding geometry

NASA Astrophysics Data System (ADS)

Reusch, Michael F.; Weissenburger, Donald W.; Nearing, James C.

1994-03-01

A simple, almost entirely analytic, method for the optimization of stress-reduced magnet-end winding paths for ribbon-like superconducting cable is presented. This technique is based on characterization of these paths as developable surfaces, i.e., surfaces whose intrinsic geometry is flat. The method is applicable to winding mandrels of arbitrary geometry. Computational searches for optimal winding paths are easily implemented via the technique. Its application to the end configuration of cylindrical Superconducting Super Collider (SSC)-type magnets is discussed. The method may be useful for other engineering problems involving the placement of thin sheets of material.

Research on Taxiway Path Optimization Based on Conflict Detection

PubMed Central

Zhou, Hang; Jiang, Xinxin

2015-01-01

Taxiway path planning is one of the effective measures to make full use of the airport resources, and the optimized paths can ensure the safety of the aircraft during the sliding process. In this paper, the taxiway path planning based on conflict detection is considered. Specific steps are shown as follows: firstly, make an improvement on A * algorithm, the conflict detection strategy is added to search for the shortest and safe path in the static taxiway network. Then, according to the sliding speed of aircraft, a time table for each node is determined and the safety interval is treated as the constraint to judge whether there is a conflict or not. The intelligent initial path planning model is established based on the results. Finally, make an example in an airport simulation environment, detect and relieve the conflict to ensure the safety. The results indicate that the model established in this paper is effective and feasible. Meanwhile, make comparison with the improved A*algorithm and other intelligent algorithms, conclude that the improved A*algorithm has great advantages. It could not only optimize taxiway path, but also ensure the safety of the sliding process and improve the operational efficiency. PMID:26226485

Research on Taxiway Path Optimization Based on Conflict Detection.

PubMed

Zhou, Hang; Jiang, Xinxin

2015-01-01

Taxiway path planning is one of the effective measures to make full use of the airport resources, and the optimized paths can ensure the safety of the aircraft during the sliding process. In this paper, the taxiway path planning based on conflict detection is considered. Specific steps are shown as follows: firstly, make an improvement on A * algorithm, the conflict detection strategy is added to search for the shortest and safe path in the static taxiway network. Then, according to the sliding speed of aircraft, a time table for each node is determined and the safety interval is treated as the constraint to judge whether there is a conflict or not. The intelligent initial path planning model is established based on the results. Finally, make an example in an airport simulation environment, detect and relieve the conflict to ensure the safety. The results indicate that the model established in this paper is effective and feasible. Meanwhile, make comparison with the improved A*algorithm and other intelligent algorithms, conclude that the improved A*algorithm has great advantages. It could not only optimize taxiway path, but also ensure the safety of the sliding process and improve the operational efficiency.

Distributed Method to Optimal Profile Descent

NASA Astrophysics Data System (ADS)

Kim, Geun I.

Current ground automation tools for Optimal Profile Descent (OPD) procedures utilize path stretching and speed profile change to maintain proper merging and spacing requirements at high traffic terminal area. However, low predictability of aircraft's vertical profile and path deviation during decent add uncertainty to computing estimated time of arrival, a key information that enables the ground control center to manage airspace traffic effectively. This paper uses an OPD procedure that is based on a constant flight path angle to increase the predictability of the vertical profile and defines an OPD optimization problem that uses both path stretching and speed profile change while largely maintaining the original OPD procedure. This problem minimizes the cumulative cost of performing OPD procedures for a group of aircraft by assigning a time cost function to each aircraft and a separation cost function to a pair of aircraft. The OPD optimization problem is then solved in a decentralized manner using dual decomposition techniques under inter-aircraft ADS-B mechanism. This method divides the optimization problem into more manageable sub-problems which are then distributed to the group of aircraft. Each aircraft solves its assigned sub-problem and communicate the solutions to other aircraft in an iterative process until an optimal solution is achieved thus decentralizing the computation of the optimization problem.

A bat algorithm with mutation for UCAV path planning.

PubMed

Wang, Gaige; Guo, Lihong; Duan, Hong; Liu, Luo; Wang, Heqi

2012-01-01

Path planning for uninhabited combat air vehicle (UCAV) is a complicated high dimension optimization problem, which mainly centralizes on optimizing the flight route considering the different kinds of constrains under complicated battle field environments. Original bat algorithm (BA) is used to solve the UCAV path planning problem. Furthermore, a new bat algorithm with mutation (BAM) is proposed to solve the UCAV path planning problem, and a modification is applied to mutate between bats during the process of the new solutions updating. Then, the UCAV can find the safe path by connecting the chosen nodes of the coordinates while avoiding the threat areas and costing minimum fuel. This new approach can accelerate the global convergence speed while preserving the strong robustness of the basic BA. The realization procedure for original BA and this improved metaheuristic approach BAM is also presented. To prove the performance of this proposed metaheuristic method, BAM is compared with BA and other population-based optimization methods, such as ACO, BBO, DE, ES, GA, PBIL, PSO, and SGA. The experiment shows that the proposed approach is more effective and feasible in UCAV path planning than the other models.

Unified path integral approach to theories of diffusion-influenced reactions

NASA Astrophysics Data System (ADS)

Prüstel, Thorsten; Meier-Schellersheim, Martin

2017-08-01

Building on mathematical similarities between quantum mechanics and theories of diffusion-influenced reactions, we develop a general approach for computational modeling of diffusion-influenced reactions that is capable of capturing not only the classical Smoluchowski picture but also alternative theories, as is here exemplified by a volume reactivity model. In particular, we prove the path decomposition expansion of various Green's functions describing the irreversible and reversible reaction of an isolated pair of molecules. To this end, we exploit a connection between boundary value and interaction potential problems with δ - and δ'-function perturbation. We employ a known path-integral-based summation of a perturbation series to derive a number of exact identities relating propagators and survival probabilities satisfying different boundary conditions in a unified and systematic manner. Furthermore, we show how the path decomposition expansion represents the propagator as a product of three factors in the Laplace domain that correspond to quantities figuring prominently in stochastic spatially resolved simulation algorithms. This analysis will thus be useful for the interpretation of current and the design of future algorithms. Finally, we discuss the relation between the general approach and the theory of Brownian functionals and calculate the mean residence time for the case of irreversible and reversible reactions.

Neighboring extremals of dynamic optimization problems with path equality constraints

NASA Technical Reports Server (NTRS)

Lee, A. Y.

1988-01-01

Neighboring extremals of dynamic optimization problems with path equality constraints and with an unknown parameter vector are considered in this paper. With some simplifications, the problem is reduced to solving a linear, time-varying two-point boundary-value problem with integral path equality constraints. A modified backward sweep method is used to solve this problem. Two example problems are solved to illustrate the validity and usefulness of the solution technique.

Cooperative path planning for multi-USV based on improved artificial bee colony algorithm

NASA Astrophysics Data System (ADS)

Cao, Lu; Chen, Qiwei

2018-03-01

Due to the complex constraints, more uncertain factors and critical real-time demand of path planning for multiple unmanned surface vehicle (multi-USV), an improved artificial bee colony (I-ABC) algorithm were proposed to solve the model of cooperative path planning for multi-USV. First the Voronoi diagram of battle field space is conceived to generate the optimal area of USVs paths. Then the chaotic searching algorithm is used to initialize the collection of paths, which is regard as foods of the ABC algorithm. With the limited data, the initial collection can search the optimal area of paths perfectly. Finally simulations of the multi-USV path planning under various threats have been carried out. Simulation results verify that the I-ABC algorithm can improve the diversity of nectar source and the convergence rate of algorithm. It can increase the adaptability of dynamic battlefield and unexpected threats for USV.

Adaptively biased sequential importance sampling for rare events in reaction networks with comparison to exact solutions from finite buffer dCME method

PubMed Central

Cao, Youfang; Liang, Jie

2013-01-01

Critical events that occur rarely in biological processes are of great importance, but are challenging to study using Monte Carlo simulation. By introducing biases to reaction selection and reaction rates, weighted stochastic simulation algorithms based on importance sampling allow rare events to be sampled more effectively. However, existing methods do not address the important issue of barrier crossing, which often arises from multistable networks and systems with complex probability landscape. In addition, the proliferation of parameters and the associated computing cost pose significant problems. Here we introduce a general theoretical framework for obtaining optimized biases in sampling individual reactions for estimating probabilities of rare events. We further describe a practical algorithm called adaptively biased sequential importance sampling (ABSIS) method for efficient probability estimation. By adopting a look-ahead strategy and by enumerating short paths from the current state, we estimate the reaction-specific and state-specific forward and backward moving probabilities of the system, which are then used to bias reaction selections. The ABSIS algorithm can automatically detect barrier-crossing regions, and can adjust bias adaptively at different steps of the sampling process, with bias determined by the outcome of exhaustively generated short paths. In addition, there are only two bias parameters to be determined, regardless of the number of the reactions and the complexity of the network. We have applied the ABSIS method to four biochemical networks: the birth-death process, the reversible isomerization, the bistable Schlögl model, and the enzymatic futile cycle model. For comparison, we have also applied the finite buffer discrete chemical master equation (dCME) method recently developed to obtain exact numerical solutions of the underlying discrete chemical master equations of these problems. This allows us to assess sampling results objectively by comparing simulation results with true answers. Overall, ABSIS can accurately and efficiently estimate rare event probabilities for all examples, often with smaller variance than other importance sampling algorithms. The ABSIS method is general and can be applied to study rare events of other stochastic networks with complex probability landscape. PMID:23862966

Adaptively biased sequential importance sampling for rare events in reaction networks with comparison to exact solutions from finite buffer dCME method

NASA Astrophysics Data System (ADS)

Cao, Youfang; Liang, Jie

2013-07-01

Critical events that occur rarely in biological processes are of great importance, but are challenging to study using Monte Carlo simulation. By introducing biases to reaction selection and reaction rates, weighted stochastic simulation algorithms based on importance sampling allow rare events to be sampled more effectively. However, existing methods do not address the important issue of barrier crossing, which often arises from multistable networks and systems with complex probability landscape. In addition, the proliferation of parameters and the associated computing cost pose significant problems. Here we introduce a general theoretical framework for obtaining optimized biases in sampling individual reactions for estimating probabilities of rare events. We further describe a practical algorithm called adaptively biased sequential importance sampling (ABSIS) method for efficient probability estimation. By adopting a look-ahead strategy and by enumerating short paths from the current state, we estimate the reaction-specific and state-specific forward and backward moving probabilities of the system, which are then used to bias reaction selections. The ABSIS algorithm can automatically detect barrier-crossing regions, and can adjust bias adaptively at different steps of the sampling process, with bias determined by the outcome of exhaustively generated short paths. In addition, there are only two bias parameters to be determined, regardless of the number of the reactions and the complexity of the network. We have applied the ABSIS method to four biochemical networks: the birth-death process, the reversible isomerization, the bistable Schlögl model, and the enzymatic futile cycle model. For comparison, we have also applied the finite buffer discrete chemical master equation (dCME) method recently developed to obtain exact numerical solutions of the underlying discrete chemical master equations of these problems. This allows us to assess sampling results objectively by comparing simulation results with true answers. Overall, ABSIS can accurately and efficiently estimate rare event probabilities for all examples, often with smaller variance than other importance sampling algorithms. The ABSIS method is general and can be applied to study rare events of other stochastic networks with complex probability landscape.

Adaptively biased sequential importance sampling for rare events in reaction networks with comparison to exact solutions from finite buffer dCME method.

PubMed

Cao, Youfang; Liang, Jie

2013-07-14

Critical events that occur rarely in biological processes are of great importance, but are challenging to study using Monte Carlo simulation. By introducing biases to reaction selection and reaction rates, weighted stochastic simulation algorithms based on importance sampling allow rare events to be sampled more effectively. However, existing methods do not address the important issue of barrier crossing, which often arises from multistable networks and systems with complex probability landscape. In addition, the proliferation of parameters and the associated computing cost pose significant problems. Here we introduce a general theoretical framework for obtaining optimized biases in sampling individual reactions for estimating probabilities of rare events. We further describe a practical algorithm called adaptively biased sequential importance sampling (ABSIS) method for efficient probability estimation. By adopting a look-ahead strategy and by enumerating short paths from the current state, we estimate the reaction-specific and state-specific forward and backward moving probabilities of the system, which are then used to bias reaction selections. The ABSIS algorithm can automatically detect barrier-crossing regions, and can adjust bias adaptively at different steps of the sampling process, with bias determined by the outcome of exhaustively generated short paths. In addition, there are only two bias parameters to be determined, regardless of the number of the reactions and the complexity of the network. We have applied the ABSIS method to four biochemical networks: the birth-death process, the reversible isomerization, the bistable Schlögl model, and the enzymatic futile cycle model. For comparison, we have also applied the finite buffer discrete chemical master equation (dCME) method recently developed to obtain exact numerical solutions of the underlying discrete chemical master equations of these problems. This allows us to assess sampling results objectively by comparing simulation results with true answers. Overall, ABSIS can accurately and efficiently estimate rare event probabilities for all examples, often with smaller variance than other importance sampling algorithms. The ABSIS method is general and can be applied to study rare events of other stochastic networks with complex probability landscape.

Extended shortest path selection for package routing of complex networks

NASA Astrophysics Data System (ADS)

Ye, Fan; Zhang, Lei; Wang, Bing-Hong; Liu, Lu; Zhang, Xing-Yi

The routing strategy plays a very important role in complex networks such as Internet system and Peer-to-Peer networks. However, most of the previous work concentrates only on the path selection, e.g. Flooding and Random Walk, or finding the shortest path (SP) and rarely considering the local load information such as SP and Distance Vector Routing. Flow-based Routing mainly considers load balance and still cannot achieve best optimization. Thus, in this paper, we propose a novel dynamic routing strategy on complex network by incorporating the local load information into SP algorithm to enhance the traffic flow routing optimization. It was found that the flow in a network is greatly affected by the waiting time of the network, so we should not consider only choosing optimized path for package transformation but also consider node congestion. As a result, the packages should be transmitted with a global optimized path with smaller congestion and relatively short distance. Analysis work and simulation experiments show that the proposed algorithm can largely enhance the network flow with the maximum throughput within an acceptable calculating time. The detailed analysis of the algorithm will also be provided for explaining the efficiency.

Simulation based optimized beam velocity in additive manufacturing

NASA Astrophysics Data System (ADS)

Vignat, Frédéric; Béraud, Nicolas; Villeneuve, François

2017-08-01

Manufacturing good parts with additive technologies rely on melt pool dimension and temperature and are controlled by manufacturing strategies often decided on machine side. Strategies are built on beam path and variable energy input. Beam path are often a mix of contour and hatching strategies filling the contours at each slice. Energy input depend on beam intensity and speed and is determined from simple thermal models to control melt pool dimensions and temperature and ensure porosity free material. These models take into account variation in thermal environment such as overhanging surfaces or back and forth hatching path. However not all the situations are correctly handled and precision is limited. This paper proposes new method to determine energy input from full built chamber 3D thermal simulation. Using the results of the simulation, energy is modified to keep melt pool temperature in a predetermined range. The paper present first an experimental method to determine the optimal range of temperature. In a second part the method to optimize the beam speed from the simulation results is presented. Finally, the optimized beam path is tested in the EBM machine and built part are compared with part built with ordinary beam path.

Generalized gradient algorithm for trajectory optimization

NASA Technical Reports Server (NTRS)

Zhao, Yiyuan; Bryson, A. E.; Slattery, R.

1990-01-01

The generalized gradient algorithm presented and verified as a basis for the solution of trajectory optimization problems improves the performance index while reducing path equality constraints, and terminal equality constraints. The algorithm is conveniently divided into two phases, of which the first, 'feasibility' phase yields a solution satisfying both path and terminal constraints, while the second, 'optimization' phase uses the results of the first phase as initial guesses.

Stepwise Catalytic Mechanism via Short-Lived Intermediate Inferred from Combined QM/MM MERP and PES Calculations on Retaining Glycosyltransferase ppGalNAcT2

PubMed Central

Trnka, Tomáš; Kozmon, Stanislav; Tvaroška, Igor; Koča, Jaroslav

2015-01-01

The glycosylation of cell surface proteins plays a crucial role in a multitude of biological processes, such as cell adhesion and recognition. To understand the process of protein glycosylation, the reaction mechanisms of the participating enzymes need to be known. However, the reaction mechanism of retaining glycosyltransferases has not yet been sufficiently explained. Here we investigated the catalytic mechanism of human isoform 2 of the retaining glycosyltransferase polypeptide UDP-GalNAc transferase by coupling two different QM/MM-based approaches, namely a potential energy surface scan in two distance difference dimensions and a minimum energy reaction path optimisation using the Nudged Elastic Band method. Potential energy scan studies often suffer from inadequate sampling of reactive processes due to a predefined scan coordinate system. At the same time, path optimisation methods enable the sampling of a virtually unlimited number of dimensions, but their results cannot be unambiguously interpreted without knowledge of the potential energy surface. By combining these methods, we have been able to eliminate the most significant sources of potential errors inherent to each of these approaches. The structural model is based on the crystal structure of human isoform 2. In the QM/MM method, the QM region consists of 275 atoms, the remaining 5776 atoms were in the MM region. We found that ppGalNAcT2 catalyzes a same-face nucleophilic substitution with internal return (SNi). The optimized transition state for the reaction is 13.8 kcal/mol higher in energy than the reactant while the energy of the product complex is 6.7 kcal/mol lower. During the process of nucleophilic attack, a proton is synchronously transferred to the leaving phosphate. The presence of a short-lived metastable oxocarbenium intermediate is likely, as indicated by the reaction energy profiles obtained using high-level density functionals. PMID:25849117

Stepwise catalytic mechanism via short-lived intermediate inferred from combined QM/MM MERP and PES calculations on retaining glycosyltransferase ppGalNAcT2.

PubMed

Trnka, Tomáš; Kozmon, Stanislav; Tvaroška, Igor; Koča, Jaroslav

2015-04-01

The glycosylation of cell surface proteins plays a crucial role in a multitude of biological processes, such as cell adhesion and recognition. To understand the process of protein glycosylation, the reaction mechanisms of the participating enzymes need to be known. However, the reaction mechanism of retaining glycosyltransferases has not yet been sufficiently explained. Here we investigated the catalytic mechanism of human isoform 2 of the retaining glycosyltransferase polypeptide UDP-GalNAc transferase by coupling two different QM/MM-based approaches, namely a potential energy surface scan in two distance difference dimensions and a minimum energy reaction path optimisation using the Nudged Elastic Band method. Potential energy scan studies often suffer from inadequate sampling of reactive processes due to a predefined scan coordinate system. At the same time, path optimisation methods enable the sampling of a virtually unlimited number of dimensions, but their results cannot be unambiguously interpreted without knowledge of the potential energy surface. By combining these methods, we have been able to eliminate the most significant sources of potential errors inherent to each of these approaches. The structural model is based on the crystal structure of human isoform 2. In the QM/MM method, the QM region consists of 275 atoms, the remaining 5776 atoms were in the MM region. We found that ppGalNAcT2 catalyzes a same-face nucleophilic substitution with internal return (SNi). The optimized transition state for the reaction is 13.8 kcal/mol higher in energy than the reactant while the energy of the product complex is 6.7 kcal/mol lower. During the process of nucleophilic attack, a proton is synchronously transferred to the leaving phosphate. The presence of a short-lived metastable oxocarbenium intermediate is likely, as indicated by the reaction energy profiles obtained using high-level density functionals.

A Method to Analyze and Optimize the Load Sharing of Split Path Transmissions

NASA Technical Reports Server (NTRS)

Krantz, Timothy L.

1996-01-01

Split-path transmissions are promising alternatives to the common planetary transmissions for rotorcraft. Heretofore, split-path designs proposed for or used in rotorcraft have featured load-sharing devices that add undesirable weight and complexity to the designs. A method was developed to analyze and optimize the load sharing in split-path transmissions without load-sharing devices. The method uses the clocking angle as a design parameter to optimize for equal load sharing. In addition, the clocking angle tolerance necessary to maintain acceptable load sharing can be calculated. The method evaluates the effects of gear-shaft twisting and bending, tooth bending, Hertzian deformations within bearings, and movement of bearing supports on load sharing. It was used to study the NASA split-path test gearbox and the U.S. Army's Comanche helicopter main rotor gearbox. Acceptable load sharing was found to be achievable and maintainable by using proven manufacturing processes. The analytical results compare favorably to available experimental data.

Singular-Arc Time-Optimal Trajectory of Aircraft in Two-Dimensional Wind Field

NASA Technical Reports Server (NTRS)

Nguyen, Nhan

2006-01-01

This paper presents a study of a minimum time-to-climb trajectory analysis for aircraft flying in a two-dimensional altitude dependent wind field. The time optimal control problem possesses a singular control structure when the lift coefficient is taken as a control variable. A singular arc analysis is performed to obtain an optimal control solution on the singular arc. Using a time-scale separation with the flight path angle treated as a fast state, the dimensionality of the optimal control solution is reduced by eliminating the lift coefficient control. A further singular arc analysis is used to decompose the original optimal control solution into the flight path angle solution and a trajectory solution as a function of the airspeed and altitude. The optimal control solutions for the initial and final climb segments are computed using a shooting method with known starting values on the singular arc The numerical results of the shooting method show that the optimal flight path angle on the initial and final climb segments are constant. The analytical approach provides a rapid means for analyzing a time optimal trajectory for aircraft performance.

Online POMDP Algorithms for Very Large Observation Spaces

DTIC Science & Technology

2017-06-06

stochastic optimization: From sets to paths." In Advances in Neural Information Processing Systems, pp. 1585- 1593 . 2015. • Luo, Yuanfu, Haoyu Bai...and Wee Sun Lee. "Adaptive stochastic optimization: From sets to paths." In Advances in Neural Information Processing Systems, pp. 1585- 1593 . 2015

Routing and spectrum assignment based on ant colony optimization of minimum consecutiveness loss in elastic optical networks

NASA Astrophysics Data System (ADS)

Wang, Fu; Liu, Bo; Zhang, Lijia; Xin, Xiangjun; Tian, Qinghua; Zhang, Qi; Rao, Lan; Tian, Feng; Luo, Biao; Liu, Yingjun; Tang, Bao

2016-10-01

Elastic Optical Networks are considered to be a promising technology for future high-speed network. In this paper, we propose a RSA algorithm based on the ant colony optimization of minimum consecutiveness loss (ACO-MCL). Based on the effect of the spectrum consecutiveness loss on the pheromone in the ant colony optimization, the path and spectrum of the minimal impact on the network are selected for the service request. When an ant arrives at the destination node from the source node along a path, we assume that this path is selected for the request. We calculate the consecutiveness loss of candidate-neighbor link pairs along this path after the routing and spectrum assignment. Then, the networks update the pheromone according to the value of the consecutiveness loss. We save the path with the smallest value. After multiple iterations of the ant colony optimization, the final selection of the path is assigned for the request. The algorithms are simulated in different networks. The results show that ACO-MCL algorithm performs better in blocking probability and spectrum efficiency than other algorithms. Moreover, the ACO-MCL algorithm can effectively decrease spectrum fragmentation and enhance available spectrum consecutiveness. Compared with other algorithms, the ACO-MCL algorithm can reduce the blocking rate by at least 5.9% in heavy load.

Robust Path Planning and Feedback Design Under Stochastic Uncertainty

NASA Technical Reports Server (NTRS)

Blackmore, Lars

2008-01-01

Autonomous vehicles require optimal path planning algorithms to achieve mission goals while avoiding obstacles and being robust to uncertainties. The uncertainties arise from exogenous disturbances, modeling errors, and sensor noise, which can be characterized via stochastic models. Previous work defined a notion of robustness in a stochastic setting by using the concept of chance constraints. This requires that mission constraint violation can occur with a probability less than a prescribed value.In this paper we describe a novel method for optimal chance constrained path planning with feedback design. The approach optimizes both the reference trajectory to be followed and the feedback controller used to reject uncertainty. Our method extends recent results in constrained control synthesis based on convex optimization to solve control problems with nonconvex constraints. This extension is essential for path planning problems, which inherently have nonconvex obstacle avoidance constraints. Unlike previous approaches to chance constrained path planning, the new approach optimizes the feedback gain as wellas the reference trajectory.The key idea is to couple a fast, nonconvex solver that does not take into account uncertainty, with existing robust approaches that apply only to convex feasible regions. By alternating between robust and nonrobust solutions, the new algorithm guarantees convergence to a global optimum. We apply the new method to an unmanned aircraft and show simulation results that demonstrate the efficacy of the approach.

Sensory Agreement Guides Kinetic Energy Optimization of Arm Movements during Object Manipulation.

PubMed

Farshchiansadegh, Ali; Melendez-Calderon, Alejandro; Ranganathan, Rajiv; Murphey, Todd D; Mussa-Ivaldi, Ferdinando A

2016-04-01

The laws of physics establish the energetic efficiency of our movements. In some cases, like locomotion, the mechanics of the body dominate in determining the energetically optimal course of action. In other tasks, such as manipulation, energetic costs depend critically upon the variable properties of objects in the environment. Can the brain identify and follow energy-optimal motions when these motions require moving along unfamiliar trajectories? What feedback information is required for such optimal behavior to occur? To answer these questions, we asked participants to move their dominant hand between different positions while holding a virtual mechanical system with complex dynamics (a planar double pendulum). In this task, trajectories of minimum kinetic energy were along curvilinear paths. Our findings demonstrate that participants were capable of finding the energy-optimal paths, but only when provided with veridical visual and haptic information pertaining to the object, lacking which the trajectories were executed along rectilinear paths.

Path Searching Based Fault Automated Recovery Scheme for Distribution Grid with DG

NASA Astrophysics Data System (ADS)

Xia, Lin; Qun, Wang; Hui, Xue; Simeng, Zhu

2016-12-01

Applying the method of path searching based on distribution network topology in setting software has a good effect, and the path searching method containing DG power source is also applicable to the automatic generation and division of planned islands after the fault. This paper applies path searching algorithm in the automatic division of planned islands after faults: starting from the switch of fault isolation, ending in each power source, and according to the line load that the searching path traverses and the load integrated by important optimized searching path, forming optimized division scheme of planned islands that uses each DG as power source and is balanced to local important load. Finally, COBASE software and distribution network automation software applied are used to illustrate the effectiveness of the realization of such automatic restoration program.

Optimism and depression: a new look at social support as a mediator among women at risk for breast cancer.

PubMed

Garner, Melissa J; McGregor, Bonnie A; Murphy, Karly M; Koenig, Alex L; Dolan, Emily D; Albano, Denise

2015-12-01

Breast cancer risk is a chronic stressor associated with depression. Optimism is associated with lower levels of depression among breast cancer survivors. However, to our knowledge, no studies have explored the relationship between optimism and depression among women at risk for breast cancer. We hypothesized that women at risk for breast cancer who have higher levels of optimism would report lower levels of depression and that social support would mediate this relationship. Participants (N = 199) with elevated distress were recruited from the community and completed self-report measures of depression, optimism, and social support. Participants were grouped based on their family history of breast cancer. Path analysis was used to examine the cross-sectional relationship between optimism, social support, and depressive symptoms in each group. Results indicated that the variance in depressive symptoms was partially explained through direct paths from optimism and social support among women with a family history of breast cancer. The indirect path from optimism to depressive symptoms via social support was significant (β = -.053; 90% CI = -.099 to -.011, p = .037) in this group. However, among individuals without a family history of breast cancer, the indirect path from optimism to depressive symptoms via social support was not significant. These results suggest that social support partially mediates the relationship between optimism and depression among women at risk for breast cancer. Social support may be an important intervention target to reduce depression among women at risk for breast cancer. Copyright © 2015 John Wiley & Sons, Ltd.

Coupling photochemical reaction detection based on singlet oxygen sensitization to capillary electrochromatography

PubMed

Dickson; Odom; Ducheneaux; Murray; Milofsky

2000-07-15

Despite the impressive separation efficiency afforded by capillary electrochromatography (CEC), the detection of UV-absorbing compounds following separation in capillary dimensions remains limited by the short path length (5-75 microm) through the column. Moreover, analytes that are poor chromophores present an additional challenge with respect to sensitive detection in CEC. This paper illustrates a new photochemical reaction detection scheme for CEC that takes advantage of the catalytic nature of type II photooxidation reactions. The sensitive detection scheme is selective toward molecules capable of photosensitizing the formation of singlet molecular oxygen (1O2). Following separation by CEC, UV-absorbing analytes promote groundstate 3O2 to an excited state (1O2) which reacts rapidly with tert-butyl-3,4,5-trimethylpyrrolecarboxylate, which is added to the running buffer. Detection is based on the loss of pyrrole. The reaction is catalytic in nature since one analyte molecule may absorb light many times, producing large amounts of 1O2. The detection limit for 9-acetylanthracene, following separation by CEC, is approximately 6 x 10(-9) M (S/N = 3). Optimization of the factors effecting the S/N for four model compounds is discussed.

An improved hierarchical A * algorithm in the optimization of parking lots

NASA Astrophysics Data System (ADS)

Wang, Yong; Wu, Junjuan; Wang, Ying

2017-08-01

In the parking lot parking path optimization, the traditional evaluation index is the shortest distance as the best index and it does not consider the actual road conditions. Now, the introduction of a more practical evaluation index can not only simplify the hardware design of the boot system but also save the software overhead. Firstly, we establish the parking lot network graph RPCDV mathematical model and all nodes in the network is divided into two layers which were constructed using different evaluation function base on the improved hierarchical A * algorithm which improves the time optimal path search efficiency and search precision of the evaluation index. The final results show that for different sections of the program attribute parameter algorithm always faster the time to find the optimal path.

Atmospheric reaction of Cl + methacrolein: a theoretical study on the mechanism, and pressure- and temperature-dependent rate constants.

PubMed

Sun, Cuihong; Xu, Baoen; Zhang, Shaowen

2014-05-22

Methacrolein is a major degradation product of isoprene, the reaction of methacrolein with Cl atoms may play some roles in the degradation of isoprene where these species are relatively abundant. However, the energetics and kinetics of this reaction, which govern the reaction branching, are still not well understood so far. In the present study, two-dimensional potential energy surfaces were constructed to analyze the minimum energy path of the barrierless addition process between Cl and the C═C double bond of methacrolein, which reveals that the terminal addition intermediate is directly formed from the addition reaction. The terminal addition intermediate can further yield different products among which the reaction paths abstracting the aldehyde hydrogen atom and the methyl hydrogen atom are dominant reaction exits. The minimum reaction path for the direct aldehydic hydrogen atom abstraction is also obtained. The reaction kinetics was calculated by the variational transition state theory in conjunction with the master equation method. From the theoretical model we predicted that the overall rate constant of the Cl + methacrolein reaction at 297 K and atmospheric pressure is koverall = 2.3× 10(-10) cm(3) molecule(-1) s(-1), and the branching ratio of the aldehydic hydrogen abstraction is about 12%. The reaction is pressure dependent at P < 10 Torr with the high pressure limit at about 100 Torr. The calculated results could well account for the experimental observations.

Comparison of Genetic Algorithm and Hill Climbing for Shortest Path Optimization Mapping

NASA Astrophysics Data System (ADS)

Fronita, Mona; Gernowo, Rahmat; Gunawan, Vincencius

2018-02-01

Traveling Salesman Problem (TSP) is an optimization to find the shortest path to reach several destinations in one trip without passing through the same city and back again to the early departure city, the process is applied to the delivery systems. This comparison is done using two methods, namely optimization genetic algorithm and hill climbing. Hill Climbing works by directly selecting a new path that is exchanged with the neighbour's to get the track distance smaller than the previous track, without testing. Genetic algorithms depend on the input parameters, they are the number of population, the probability of crossover, mutation probability and the number of generations. To simplify the process of determining the shortest path supported by the development of software that uses the google map API. Tests carried out as much as 20 times with the number of city 8, 16, 24 and 32 to see which method is optimal in terms of distance and time computation. Based on experiments conducted with a number of cities 3, 4, 5 and 6 producing the same value and optimal distance for the genetic algorithm and hill climbing, the value of this distance begins to differ with the number of city 7. The overall results shows that these tests, hill climbing are more optimal to number of small cities and the number of cities over 30 optimized using genetic algorithms.

A new optimal seam method for seamless image stitching

NASA Astrophysics Data System (ADS)

Xue, Jiale; Chen, Shengyong; Cheng, Xu; Han, Ying; Zhao, Meng

2017-07-01

A novel optimal seam method which aims to stitch those images with overlapping area more seamlessly has been propos ed. Considering the traditional gradient domain optimal seam method and fusion algorithm result in bad color difference measurement and taking a long time respectively, the input images would be converted to HSV space and a new energy function is designed to seek optimal stitching path. To smooth the optimal stitching path, a simplified pixel correction and weighted average method are utilized individually. The proposed methods exhibit performance in eliminating the stitching seam compared with the traditional gradient optimal seam and high efficiency with multi-band blending algorithm.

A Bat Algorithm with Mutation for UCAV Path Planning

PubMed Central

Wang, Gaige; Guo, Lihong; Duan, Hong; Liu, Luo; Wang, Heqi

2012-01-01

Path planning for uninhabited combat air vehicle (UCAV) is a complicated high dimension optimization problem, which mainly centralizes on optimizing the flight route considering the different kinds of constrains under complicated battle field environments. Original bat algorithm (BA) is used to solve the UCAV path planning problem. Furthermore, a new bat algorithm with mutation (BAM) is proposed to solve the UCAV path planning problem, and a modification is applied to mutate between bats during the process of the new solutions updating. Then, the UCAV can find the safe path by connecting the chosen nodes of the coordinates while avoiding the threat areas and costing minimum fuel. This new approach can accelerate the global convergence speed while preserving the strong robustness of the basic BA. The realization procedure for original BA and this improved metaheuristic approach BAM is also presented. To prove the performance of this proposed metaheuristic method, BAM is compared with BA and other population-based optimization methods, such as ACO, BBO, DE, ES, GA, PBIL, PSO, and SGA. The experiment shows that the proposed approach is more effective and feasible in UCAV path planning than the other models. PMID:23365518

Ab initio computational study of reaction mechanism of peptide bond formation on HF/6-31G(d,p) level

NASA Astrophysics Data System (ADS)

Siahaan, P.; Lalita, M. N. T.; Cahyono, B.; Laksitorini, M. D.; Hildayani, S. Z.

2017-02-01

Peptide plays an important role in modulation of various cell functions. Therefore, formation reaction of the peptide is important for chemical reactions. One way to probe the reaction of peptide synthesis is a computational method. The purpose of this research is to determine the reaction mechanism for peptide bond formation on Ac-PV-NH2 and Ac-VP-NH2 synthesis from amino acid proline and valine by ab initio computational approach. The calculations were carried out by theory and basis set HF/6-31G(d,p) for four mechanisms (path 1 to 4) that proposed in this research. The results show that the highest of the rate determining step between reactant and transition state (TS) for path 1, 2, 3, and 4 are 163.06 kJ.mol-1, 1868 kJ.mol-1, 5685 kJ.mol-1, and 1837 kJ.mol-1. The calculation shows that the most preferred reaction of Ac-PV-NH2 and Ac-VP-NH2 synthesis from amino acid proline and valine are on the path 1 (initiated with the termination of H+ in proline amino acid) that produce Ac-PV-NH2.

Geometric phase effects in ultracold chemistry

NASA Astrophysics Data System (ADS)

Hazra, Jisha; Naduvalath, Balakrishnan; Kendrick, Brian K.

2016-05-01

In molecules, the geometric phase, also known as Berry's phase, originates from the adiabatic transport of the electronic wavefunction when the nuclei follow a closed path encircling a conical intersection between two electronic potential energy surfaces. It is demonstrated that the inclusion of the geometric phase has an important effect on ultracold chemical reaction rates. The effect appears in rotationally and vibrationally resolved integral cross sections as well as cross sections summed over all product quantum states. It arises from interference between scattering amplitudes of two reaction pathways: a direct path and a looping path that encircle the conical intersection between the two lowest adiabatic electronic potential energy surfaces. Illustrative results are presented for the O+ OH --> H+ O2 reaction and for hydrogen exchange in H+ H2 and D+HD reactions. It is also qualitatively demonstrated that the geometric phase effect can be modulated by applying an external electric field allowing the possibility of quantum control of chemical reactions in the ultracold regime. This work was supported in part by NSF Grant PHY-1505557 (N.B.) and ARO MURI Grant No. W911NF-12-1-0476 (N.B.).

An Optimization Principle for Deriving Nonequilibrium Statistical Models of Hamiltonian Dynamics

NASA Astrophysics Data System (ADS)

Turkington, Bruce

2013-08-01

A general method for deriving closed reduced models of Hamiltonian dynamical systems is developed using techniques from optimization and statistical estimation. Given a vector of resolved variables, selected to describe the macroscopic state of the system, a family of quasi-equilibrium probability densities on phase space corresponding to the resolved variables is employed as a statistical model, and the evolution of the mean resolved vector is estimated by optimizing over paths of these densities. Specifically, a cost function is constructed to quantify the lack-of-fit to the microscopic dynamics of any feasible path of densities from the statistical model; it is an ensemble-averaged, weighted, squared-norm of the residual that results from submitting the path of densities to the Liouville equation. The path that minimizes the time integral of the cost function determines the best-fit evolution of the mean resolved vector. The closed reduced equations satisfied by the optimal path are derived by Hamilton-Jacobi theory. When expressed in terms of the macroscopic variables, these equations have the generic structure of governing equations for nonequilibrium thermodynamics. In particular, the value function for the optimization principle coincides with the dissipation potential that defines the relation between thermodynamic forces and fluxes. The adjustable closure parameters in the best-fit reduced equations depend explicitly on the arbitrary weights that enter into the lack-of-fit cost function. Two particular model reductions are outlined to illustrate the general method. In each example the set of weights in the optimization principle contracts into a single effective closure parameter.

Modified dwell time optimization model and its applications in subaperture polishing.

PubMed

Dong, Zhichao; Cheng, Haobo; Tam, Hon-Yuen

2014-05-20

The optimization of dwell time is an important procedure in deterministic subaperture polishing. We present a modified optimization model of dwell time by iterative and numerical method, assisted by extended surface forms and tool paths for suppressing the edge effect. Compared with discrete convolution and linear equation models, the proposed model has essential compatibility with arbitrary tool paths, multiple tool influence functions (TIFs) in one optimization, and asymmetric TIFs. The emulational fabrication of a Φ200  mm workpiece by the proposed model yields a smooth, continuous, and non-negative dwell time map with a root-mean-square (RMS) convergence rate of 99.6%, and the optimization costs much less time. By the proposed model, influences of TIF size and path interval to convergence rate and polishing time are optimized, respectively, for typical low and middle spatial-frequency errors. Results show that (1) the TIF size is nonlinear inversely proportional to convergence rate and polishing time. A TIF size of ~1/7 workpiece size is preferred; (2) the polishing time is less sensitive to path interval, but increasing the interval markedly reduces the convergence rate. A path interval of ~1/8-1/10 of the TIF size is deemed to be appropriate. The proposed model is deployed on a JR-1800 and MRF-180 machine. Figuring results of Φ920  mm Zerodur paraboloid and Φ100  mm Zerodur plane by them yield RMS of 0.016λ and 0.013λ (λ=632.8  nm), respectively, and thereby validate the feasibility of proposed dwell time model used for subaperture polishing.

Robust Video Stabilization Using Particle Keypoint Update and l1-Optimized Camera Path

PubMed Central

Jeon, Semi; Yoon, Inhye; Jang, Jinbeum; Yang, Seungji; Kim, Jisung; Paik, Joonki

2017-01-01

Acquisition of stabilized video is an important issue for various type of digital cameras. This paper presents an adaptive camera path estimation method using robust feature detection to remove shaky artifacts in a video. The proposed algorithm consists of three steps: (i) robust feature detection using particle keypoints between adjacent frames; (ii) camera path estimation and smoothing; and (iii) rendering to reconstruct a stabilized video. As a result, the proposed algorithm can estimate the optimal homography by redefining important feature points in the flat region using particle keypoints. In addition, stabilized frames with less holes can be generated from the optimal, adaptive camera path that minimizes a temporal total variation (TV). The proposed video stabilization method is suitable for enhancing the visual quality for various portable cameras and can be applied to robot vision, driving assistant systems, and visual surveillance systems. PMID:28208622

Optimization of carbon mitigation paths in the power sector of Shenzhen, China

NASA Astrophysics Data System (ADS)

Li, Xin; Hu, Guangxiao; Duan, Ying; Ji, Junping

2017-08-01

This paper studied the carbon mitigation paths of the power sector in Shenzhen, China from a supply-side perspective. We investigated the carbon mitigation potentials and investments of seventeen mitigation technologies in the power sector, and employed a linear programming method to optimize the mitigation paths. The results show that: 1) The total carbon mitigation potential is 5.95 MtCO2 in 2020 in which the adjustment of power supply structure, technical improvements of existing coal- and gas-fired power plant account for 87.5%,6.5% and 6.0%, respectively. 2) In the optimal path, the avoided carbon dioxide to meet the local government’s mitigation goal in power sector is 1.26 MtCO2.The adjustment of power supply structure and technical improvement of the coal-fired power plants are the driving factors of carbon mitigation, with contributions to total carbon mitigation are 72.6% and 27.4%, respectively.

Effect of Molecule–Surface Reaction Mechanism on the Electronic Characteristics and Photovoltaic Performance of Molecularly Modified Si

PubMed Central

2013-01-01

We report on the passivation properties of molecularly modified, oxide-free Si(111) surfaces. The reaction of 1-alcohol with the H-passivated Si(111) surface can follow two possible paths, nucleophilic substitution (SN) and radical chain reaction (RCR), depending on adsorption conditions. Moderate heating leads to the SN reaction, whereas with UV irradiation RCR dominates, with SN as a secondary path. We show that the site-sensitive SN reaction leads to better electrical passivation, as indicated by smaller surface band bending and a longer lifetime of minority carriers. However, the surface-insensitive RCR reaction leads to more dense monolayers and, therefore, to much better chemical stability, with lasting protection of the Si surface against oxidation. Thus, our study reveals an inherent dissonance between electrical and chemical passivation. Alkoxy monolayers, formed under UV irradiation, benefit, though, from both chemical and electronic passivation because under these conditions both SN and RCR occur. This is reflected in longer minority carrier lifetimes, lower reverse currents in the dark, and improved photovoltaic performance, over what is obtained if only one of the mechanisms operates. These results show how chemical kinetics and reaction paths impact electronic properties at the device level. It further suggests an approach for effective passivation of other semiconductors. PMID:24205409

Predictor laws for pictorial flight displays

NASA Technical Reports Server (NTRS)

Grunwald, A. J.

1985-01-01

Two predictor laws are formulated and analyzed: (1) a circular path law based on constant accelerations perpendicular to the path and (2) a predictor law based on state transition matrix computations. It is shown that for both methods the predictor provides the essential lead zeros for the path-following task. However, in contrast to the circular path law, the state transition matrix law furnishes the system with additional zeros that entirely cancel out the higher-frequency poles of the vehicle dynamics. On the other hand, the circular path law yields a zero steady-state error in following a curved trajectory with a constant radius. A combined predictor law is suggested that utilizes the advantages of both methods. A simple analysis shows that the optimal prediction time mainly depends on the level of precision required in the path-following task, and guidelines for determining the optimal prediction time are given.

Multi-hop path tracing of mobile robot with multi-range image

NASA Astrophysics Data System (ADS)

Choudhury, Ramakanta; Samal, Chandrakanta; Choudhury, Umakanta

2010-02-01

It is well known that image processing depends heavily upon image representation technique . This paper intends to find out the optimal path of mobile robots for a specified area where obstacles are predefined as well as modified. Here the optimal path is represented by using the Quad tree method. Since there has been rising interest in the use of quad tree, we have tried to use the successive subdivision of images into quadrants from which the quad tree is developed. In the quad tree, obstacles-free area and the partial filled area are represented with different notations. After development of quad tree the algorithm is used to find the optimal path by employing neighbor finding technique, with a view to move the robot from the source to destination. The algorithm, here , permeates through the entire tree, and tries to locate the common ancestor for computation. The computation and the algorithm, aim at easing the ability of the robot to trace the optimal path with the help of adjacencies between the neighboring nodes as well as determining such adjacencies in the horizontal, vertical and diagonal directions. In this paper efforts have been made to determine the movement of the adjacent block in the quad tree and to detect the transition between the blocks equal size and finally generate the result.

Microsolvated Model for the Kinetics and Thermodynamics of Glycosidic Bond Dissociative Cleavage of Nucleoside D4G.

PubMed

Jiang, Yang; Xue, Ying; Zeng, Yi

2018-02-15

Using the microsolvated model that involves explicit water molecules and implicit solvent in the optimization, two proposed dissociative hydrolysis mechanisms of 2',3'-didehydro-2',3'-dideoxyguanosine (d4G) have been first investigated by means of M06-2X(CPCM, water)/6-31++G(d,p) method. The glycosidic bond dissociation for the generation of the oxacarbenium ion intermediate is the rate-determining step (RDS). The subsequent nucleophilic water attack from different side of the oxacarbenium ion intermediate gives either the α-product [(2S,5S)-5-(hydroxymethyl)-2,5-dihydrofuran-2-ol] or β-product [(2R,5S)-5-(hydroxymethyl)-2,5-dihydrofuran-2-ol] and is thus referred to as α-path (inversion) and β-path (retention). Two to five explicit water molecules (n = 2-5) are considered in the microsolvated model, and n = 3 or 4 is the smallest model capable of minimizing the activation energy for α-path and β-path, respectively. Our theoretical results suggest that α-path (n = 3) is more kinetically favorable with lower free energy barrier (RDS) of 27.7 kcal mol -1 , in contrast to that of 30.7 kcal mol -1 for the β-path (n = 4). The kinetic preference of the α-path is rationalized by NBO analysis. Whereas thte β-path is more thermodynamically favorable over the α-path, where the formation of β-product and α-product are exergonic and endergonic, respectively, providing theoretical support for the experimental observation that the β-cleavage product was the major one after sufficient reaction time. Comparisons of d4G with analogous cyclo-d4G and dG from kinetic free energy barriers and thermodynamic heterolytic dissociation energies were also carried out. Our kinetic and thermodynamic results manifest that the order of glycosidic bond stability should be d4G < cyclo-d4G < dG, which agrees well with the reported experimental stability order of d4G compounds and analogues and gives further understanding on the influence of 6-cyclopropylamino and unsaturated ribose to the glycosidic bond instability of d4G.

A two-stage path planning approach for multiple car-like robots based on PH curves and a modified harmony search algorithm

NASA Astrophysics Data System (ADS)

Zeng, Wenhui; Yi, Jin; Rao, Xiao; Zheng, Yun

2017-11-01

In this article, collision-avoidance path planning for multiple car-like robots with variable motion is formulated as a two-stage objective optimization problem minimizing both the total length of all paths and the task's completion time. Accordingly, a new approach based on Pythagorean Hodograph (PH) curves and Modified Harmony Search algorithm is proposed to solve the two-stage path-planning problem subject to kinematic constraints such as velocity, acceleration, and minimum turning radius. First, a method of path planning based on PH curves for a single robot is proposed. Second, a mathematical model of the two-stage path-planning problem for multiple car-like robots with variable motion subject to kinematic constraints is constructed that the first-stage minimizes the total length of all paths and the second-stage minimizes the task's completion time. Finally, a modified harmony search algorithm is applied to solve the two-stage optimization problem. A set of experiments demonstrate the effectiveness of the proposed approach.

Interactive Learning Environment for Bio-Inspired Optimization Algorithms for UAV Path Planning

ERIC Educational Resources Information Center

Duan, Haibin; Li, Pei; Shi, Yuhui; Zhang, Xiangyin; Sun, Changhao

2015-01-01

This paper describes the development of BOLE, a MATLAB-based interactive learning environment, that facilitates the process of learning bio-inspired optimization algorithms, and that is dedicated exclusively to unmanned aerial vehicle path planning. As a complement to conventional teaching methods, BOLE is designed to help students consolidate the…

Optimizing Retransmission Threshold in Wireless Sensor Networks

PubMed Central

Bi, Ran; Li, Yingshu; Tan, Guozhen; Sun, Liang

2016-01-01

The retransmission threshold in wireless sensor networks is critical to the latency of data delivery in the networks. However, existing works on data transmission in sensor networks did not consider the optimization of the retransmission threshold, and they simply set the same retransmission threshold for all sensor nodes in advance. The method did not take link quality and delay requirement into account, which decreases the probability of a packet passing its delivery path within a given deadline. This paper investigates the problem of finding optimal retransmission thresholds for relay nodes along a delivery path in a sensor network. The object of optimizing retransmission thresholds is to maximize the summation of the probability of the packet being successfully delivered to the next relay node or destination node in time. A dynamic programming-based distributed algorithm for finding optimal retransmission thresholds for relay nodes along a delivery path in the sensor network is proposed. The time complexity is OnΔ·max1≤i≤n{ui}, where ui is the given upper bound of the retransmission threshold of sensor node i in a given delivery path, n is the length of the delivery path and Δ is the given upper bound of the transmission delay of the delivery path. If Δ is greater than the polynomial, to reduce the time complexity, a linear programming-based (1+pmin)-approximation algorithm is proposed. Furthermore, when the ranges of the upper and lower bounds of retransmission thresholds are big enough, a Lagrange multiplier-based distributed O(1)-approximation algorithm with time complexity O(1) is proposed. Experimental results show that the proposed algorithms have better performance. PMID:27171092

Quantum Mechanics and Molecular Mechanics Study of the Catalytic Mechanism of Human AMSH-LP Domain Deubiquitinating Enzymes.

PubMed

Zhu, Wenyou; Liu, Yongjun; Ling, Baoping

2015-08-25

Deubiquitinating enzymes (DUBs) catalyze the cleavage of the isopeptide bond in polyubiquitin chains to control and regulate the deubiquitination process in all known eukaryotic cells. The human AMSH-LP DUB domain specifically cleaves the isopeptide bonds in the Lys63-linked polyubiquitin chains. In this article, the catalytic mechanism of AMSH-LP has been studied using a combined quantum mechanics and molecular mechanics method. Two possible hydrolysis processes (Path 1 and Path 2) have been considered. Our calculation results reveal that the activation of Zn(2+)-coordinated water molecule is the essential step for the hydrolysis of isopeptide bond. In Path 1, the generated hydroxyl first attacks the carbonyl group of Gly76, and then the amino group of Lys63 is protonated, which is calculated to be the rate limiting step with an energy barrier of 13.1 kcal/mol. The energy barrier of the rate limiting step and the structures of intermediate and product are in agreement with the experimental results. In Path 2, the protonation of amino group of Lys63 is prior to the nucleophilic attack of activated hydroxyl. The two proton transfer processes in Path 2 correspond to comparable overall barriers (33.4 and 36.1 kcal/mol), which are very high for an enzymatic reaction. Thus, Path 2 can be ruled out. During the reaction, Glu292 acts as a proton transfer mediator, and Ser357 mainly plays a role in stabilizing the negative charge of Gly76. Besides acting as a Lewis acid, Zn(2+) also influences the reaction by coordinating to the reaction substrates (W1 and Gly76).

Spectral gap optimization of order parameters for sampling complex molecular systems

PubMed Central

Tiwary, Pratyush; Berne, B. J.

2016-01-01

In modern-day simulations of many-body systems, much of the computational complexity is shifted to the identification of slowly changing molecular order parameters called collective variables (CVs) or reaction coordinates. A vast array of enhanced-sampling methods are based on the identification and biasing of these low-dimensional order parameters, whose fluctuations are important in driving rare events of interest. Here, we describe a new algorithm for finding optimal low-dimensional CVs for use in enhanced-sampling biasing methods like umbrella sampling, metadynamics, and related methods, when limited prior static and dynamic information is known about the system, and a much larger set of candidate CVs is specified. The algorithm involves estimating the best combination of these candidate CVs, as quantified by a maximum path entropy estimate of the spectral gap for dynamics viewed as a function of that CV. The algorithm is called spectral gap optimization of order parameters (SGOOP). Through multiple practical examples, we show how this postprocessing procedure can lead to optimization of CV and several orders of magnitude improvement in the convergence of the free energy calculated through metadynamics, essentially giving the ability to extract useful information even from unsuccessful metadynamics runs. PMID:26929365

Robust Accurate Non-Invasive Analyte Monitor

DOEpatents

Robinson, Mark R.

1998-11-03

An improved method and apparatus for determining noninvasively and in vivo one or more unknown values of a known characteristic, particularly the concentration of an analyte in human tissue. The method includes: (1) irradiating the tissue with infrared energy (400 nm-2400 nm) having at least several wavelengths in a given range of wavelengths so that there is differential absorption of at least some of the wavelengths by the tissue as a function of the wavelengths and the known characteristic, the differential absorption causeing intensity variations of the wavelengths incident from the tissue; (2) providing a first path through the tissue; (3) optimizing the first path for a first sub-region of the range of wavelengths to maximize the differential absorption by at least some of the wavelengths in the first sub-region; (4) providing a second path through the tissue; and (5) optimizing the second path for a second sub-region of the range, to maximize the differential absorption by at least some of the wavelengths in the second sub-region. In the preferred embodiment a third path through the tissue is provided for, which path is optimized for a third sub-region of the range. With this arrangement, spectral variations which are the result of tissue differences (e.g., melanin and temperature) can be reduced. At least one of the paths represents a partial transmission path through the tissue. This partial transmission path may pass through the nail of a finger once and, preferably, twice. Also included are apparatus for: (1) reducing the arterial pulsations within the tissue; and (2) maximizing the blood content i the tissue.

Mixed quantum-classical studies of energy partitioning in unimolecular chemical reactions

NASA Astrophysics Data System (ADS)

Bladow, Landon Lowell

A mixed quantum-classical reaction path Hamiltonian method is utilized to study the dynamics of unimolecular reactions. The method treats motion along the reaction path classically and treats the transverse vibrations quantum mechanically. The theory leads to equations that predict the disposai of the exit-channel potential energy to product translation and vibration. In addition, vibrational state distributions are obtained for the product normal modes. Vibrational excitation results from the curvature of the minimum energy reaction path. The method is applied to six unimolecular reactions: HF elimination from fluoroethane, 1,1-difluoroethane, 1,1-difluoroethene, and trifluoromethane; and HCl elimination from chloroethane and acetyl chloride. The minimum energy paths were calculated at either the MP2 or B3LYP level of theory. In all cases, the majority of the vibrational excitation of the products occurs in the HX fragment. The results are compared to experimental data and other theoretical results, where available. The best agreement between the experimental and calculated HX vibrational distributions is found for the halogenated ethanes, and the experimental deduction that the majority of the HX vibrational excitation arises from the potential energy release is supported. It is believed that the excess energy provided in experiments contributes to the poorer agreement between experiment and theory observed for HF elimination from 1,1-difluoroethene and trifluoromethane. An attempt is described to incorporate a treatment of the excess energy into the present method. However, the sign of the curvature coupling elements is then found to affect the dynamics. Overall, the method appears to be an efficient dynamical tool for modeling the disposal of the exit-channel potential energy in unimolecular reactions.

The potential role of magmatic gases in the genesis of Illinois- Kentucky fluorspar deposits: implications from chemical reaction path modeling

USGS Publications Warehouse

Plumlee, G.S.; Goldhaber, M.B.; Rowan, E.L.

1995-01-01

Presents results of reaction path calculations using the chemical speciation and reaction path program SOLVEQ and CHILLER to model possible fluorite deposition mechanisms in the Illinois-Kentucky fluorspar district. The results indicate that the fluids responsible for Illinois-Kentucky fluorspar mineralization were most likely quite acidic (pH < 4) and rich in fluorine in order to produce the fluorite-rich, dolomite-poor mineral assemblages and extensive dissolution of host limestones. A possible source for the acid and fluorine may have been HF-rich gases which were expelled from alkalic magmas and then incorporated by migrating basinal brines. An analysis of the geologic setting of other fluorite deposits and districts worldwide suggests that involvement of magmatic gases is probable for many of these districts as well. -from Authors

CO oxidation reaction on Pt(111) studied by the dynamic Monte Carlo method including lateral interactions of adsorbates.

PubMed

Nagasaka, Masanari; Kondoh, Hiroshi; Nakai, Ikuyo; Ohta, Toshiaki

2007-01-28

The dynamics of adsorbate structures during CO oxidation on Pt(111) surfaces and its effects on the reaction were studied by the dynamic Monte Carlo method including lateral interactions of adsorbates. The lateral interaction energies between adsorbed species were calculated by the density functional theory method. Dynamic Monte Carlo simulations were performed for the oxidation reaction over a mesoscopic scale, where the experimentally determined activation energies of elementary paths were altered by the calculated lateral interaction energies. The simulated results reproduced the characteristics of the microscopic and mesoscopic scale adsorbate structures formed during the reaction, and revealed that the complicated reaction kinetics is comprehensively explained by a single reaction path affected by the surrounding adsorbates. We also propose from the simulations that weakly adsorbed CO molecules at domain boundaries promote the island-periphery specific reaction.

Kinetic constrained optimization of the golf swing hub path.

PubMed

Nesbit, Steven M; McGinnis, Ryan S

2014-12-01

This study details an optimization of the golf swing, where the hand path and club angular trajectories are manipulated. The optimization goal was to maximize club head velocity at impact within the interaction kinetic limitations (force, torque, work, and power) of the golfer as determined through the analysis of a typical swing using a two-dimensional dynamic model. The study was applied to four subjects with diverse swing capabilities and styles. It was determined that it is possible for all subjects to increase their club head velocity at impact within their respective kinetic limitations through combined modifications to their respective hand path and club angular trajectories. The manner of the modifications, the degree of velocity improvement, the amount of kinetic reduction, and the associated kinetic limitation quantities were subject dependent. By artificially minimizing selected kinetic inputs within the optimization algorithm, it was possible to identify swing trajectory characteristics that indicated relative kinetic weaknesses of a subject. Practical implications are offered based upon the findings of the study. Key PointsThe hand path trajectory is an important characteristic of the golf swing and greatly affects club head velocity and golfer/club energy transfer.It is possible to increase the energy transfer from the golfer to the club by modifying the hand path and swing trajectories without increasing the kinetic output demands on the golfer.It is possible to identify relative kinetic output strengths and weakness of a golfer through assessment of the hand path and swing trajectories.Increasing any one of the kinetic outputs of the golfer can potentially increase the club head velocity at impact.The hand path trajectory has important influences over the club swing trajectory.

Kinetic Constrained Optimization of the Golf Swing Hub Path

PubMed Central

Nesbit, Steven M.; McGinnis, Ryan S.

2014-01-01

This study details an optimization of the golf swing, where the hand path and club angular trajectories are manipulated. The optimization goal was to maximize club head velocity at impact within the interaction kinetic limitations (force, torque, work, and power) of the golfer as determined through the analysis of a typical swing using a two-dimensional dynamic model. The study was applied to four subjects with diverse swing capabilities and styles. It was determined that it is possible for all subjects to increase their club head velocity at impact within their respective kinetic limitations through combined modifications to their respective hand path and club angular trajectories. The manner of the modifications, the degree of velocity improvement, the amount of kinetic reduction, and the associated kinetic limitation quantities were subject dependent. By artificially minimizing selected kinetic inputs within the optimization algorithm, it was possible to identify swing trajectory characteristics that indicated relative kinetic weaknesses of a subject. Practical implications are offered based upon the findings of the study. Key Points The hand path trajectory is an important characteristic of the golf swing and greatly affects club head velocity and golfer/club energy transfer. It is possible to increase the energy transfer from the golfer to the club by modifying the hand path and swing trajectories without increasing the kinetic output demands on the golfer. It is possible to identify relative kinetic output strengths and weakness of a golfer through assessment of the hand path and swing trajectories. Increasing any one of the kinetic outputs of the golfer can potentially increase the club head velocity at impact. The hand path trajectory has important influences over the club swing trajectory. PMID:25435779

Using the Gurobi Solvers on the Peregrine System | High-Performance

Science.gov Websites

Peregrine System Gurobi Optimizer is a suite of solvers for mathematical programming. It is licensed for ('GRB_MATLAB_PATH') >> path(path,grb) Gurobi and GAMS GAMS is a high-level modeling system for mathematical

An Optimization-Driven Analysis Pipeline to Uncover Biomarkers and Signaling Paths: Cervix Cancer.

PubMed

Lorenzo, Enery; Camacho-Caceres, Katia; Ropelewski, Alexander J; Rosas, Juan; Ortiz-Mojer, Michael; Perez-Marty, Lynn; Irizarry, Juan; Gonzalez, Valerie; Rodríguez, Jesús A; Cabrera-Rios, Mauricio; Isaza, Clara

2015-06-01

Establishing how a series of potentially important genes might relate to each other is relevant to understand the origin and evolution of illnesses, such as cancer. High-throughput biological experiments have played a critical role in providing information in this regard. A special challenge, however, is that of trying to conciliate information from separate microarray experiments to build a potential genetic signaling path. This work proposes a two-step analysis pipeline, based on optimization, to approach meta-analysis aiming to build a proxy for a genetic signaling path.

Optimal Patrol to Detect Attacks at Dispersed Heterogeneous Locations

DTIC Science & Technology

2013-12-01

path with one revisit SPR2 Shortest path with two revisits SPR3 Shortest path with three revisits TSP Traveling salesman problem UAV Unmanned aerial...path patrol pattern. Finding the shortest-path patrol pattern is an example of solving a traveling salesman problem , as described in Section 16.5 of...use of patrol paths based on the traveling salesman prob- lem (TSP), where patrollers follow the shortest Hamiltonian cycle in a graph in order to

Corrections to scaling for watersheds, optimal path cracks, and bridge lines

NASA Astrophysics Data System (ADS)

Fehr, E.; Schrenk, K. J.; Araújo, N. A. M.; Kadau, D.; Grassberger, P.; Andrade, J. S., Jr.; Herrmann, H. J.

2012-07-01

We study the corrections to scaling for the mass of the watershed, the bridge line, and the optimal path crack in two and three dimensions (2D and 3D). We disclose that these models have numerically equivalent fractal dimensions and leading correction-to-scaling exponents. We conjecture all three models to possess the same fractal dimension, namely, df=1.2168±0.0005 in 2D and df=2.487±0.003 in 3D, and the same exponent of the leading correction, Ω=0.9±0.1 and Ω=1.0±0.1, respectively. The close relations between watersheds, optimal path cracks in the strong disorder limit, and bridge lines are further supported by either heuristic or exact arguments.

Modeling of tool path for the CNC sheet cutting machines

NASA Astrophysics Data System (ADS)

Petunin, Aleksandr A.

2015-11-01

In the paper the problem of tool path optimization for CNC (Computer Numerical Control) cutting machines is considered. The classification of the cutting techniques is offered. We also propose a new classification of toll path problems. The tasks of cost minimization and time minimization for standard cutting technique (Continuous Cutting Problem, CCP) and for one of non-standard cutting techniques (Segment Continuous Cutting Problem, SCCP) are formalized. We show that the optimization tasks can be interpreted as discrete optimization problem (generalized travel salesman problem with additional constraints, GTSP). Formalization of some constraints for these tasks is described. For the solution GTSP we offer to use mathematical model of Prof. Chentsov based on concept of a megalopolis and dynamic programming.

Metabolic PathFinding: inferring relevant pathways in biochemical networks.

PubMed

Croes, Didier; Couche, Fabian; Wodak, Shoshana J; van Helden, Jacques

2005-07-01

Our knowledge of metabolism can be represented as a network comprising several thousands of nodes (compounds and reactions). Several groups applied graph theory to analyse the topological properties of this network and to infer metabolic pathways by path finding. This is, however, not straightforward, with a major problem caused by traversing irrelevant shortcuts through highly connected nodes, which correspond to pool metabolites and co-factors (e.g. H2O, NADP and H+). In this study, we present a web server implementing two simple approaches, which circumvent this problem, thereby improving the relevance of the inferred pathways. In the simplest approach, the shortest path is computed, while filtering out the selection of highly connected compounds. In the second approach, the shortest path is computed on the weighted metabolic graph where each compound is assigned a weight equal to its connectivity in the network. This approach significantly increases the accuracy of the inferred pathways, enabling the correct inference of relatively long pathways (e.g. with as many as eight intermediate reactions). Available options include the calculation of the k-shortest paths between two specified seed nodes (either compounds or reactions). Multiple requests can be submitted in a queue. Results are returned by email, in textual as well as graphical formats (available in http://www.scmbb.ulb.ac.be/pathfinding/).

TU-G-BRB-01: Continuous Path Optimization for Non-Coplanar Variant SAD IMRT Delivery Using C-Arm Machines.

PubMed

Ruan, D; Dong, P; Low, D; Sheng, K

2012-06-01

To develop and investigate a continuous path optimization methodology to traverse prescribed non-coplanar IMRT beams with variant SADs, by orchestrating the couch and gantry movement with zero-collision, minimal patient motion consequence and machine travel time. We convert the given collision zone definition and the prescribed beam location/angles to a tumor-centric coordinate, and represent the traversing path as a continuous open curve. We proceed to optimize a composite objective function consisting of (1) a strong attraction energy to ensure all prescribed beams are en-route, (2) a penalty for patient-motion inducing couch motion, and (3) a penalty for travel-time inducing overall path-length. Feasibility manifold is defined as complement to collision zone and the optimization is performed with a level set representation evolved with variational flows. The proposed method has been implemented and tested on clinically derived data. In the absence of any existing solutions for the same problem, we validate by: (1) visual inspecting the generated path rendered in the 3D tumor-centric coordinates, and (2) comparing with a traveling-salesman (TSP) solution obtained from relaxing the variant SADs and continuous collision-avoidance requirement. The proposed method has generated delivery paths that are smooth and intuitively appealing. Under relaxed settings, our results outperform the generic TSP solutions and agree with specially tuned versions. We have proposed a novel systematic approach that automatically determines the continuous path to cover non-coplanar, varying SAD IMRT beams. The proposed approach accommodates patient-specific collision zone definition and ensures its avoidance continuously. The differential penalty to couch and gantry motions allows customizable tradeoff between patient geometry stability and delivery efficiency. This development paves the path to achieve safe, accurate and efficient non-coplanar IMRT delivery with the advanced robotic controls in new-generation C-arm systems, enabling practical harvesting of the dose benefit offered by non-coplanar, variant SAD IMRT treatment. © 2012 American Association of Physicists in Medicine.

Applicability of PM3 to transphosphorylation reaction path: Toward designing a minimal ribozyme

NASA Technical Reports Server (NTRS)

Manchester, John I.; Shibata, Masayuki; Setlik, Robert F.; Ornstein, Rick L.; Rein, Robert

1993-01-01

A growing body of evidence shows that RNA can catalyze many of the reactions necessary both for replication of genetic material and the possible transition into the modern protein-based world. However, contemporary ribozymes are too large to have self-assembled from a prebiotic oligonucleotide pool. Still, it is likely that the major features of the earliest ribozymes have been preserved as molecular fossils in the catalytic RNA of today. Therefore, the search for a minimal ribozyme has been aimed at finding the necessary structural features of a modern ribozyme (Beaudry and Joyce, 1990). Both a three-dimensional model and quantum chemical calculations are required to quantitatively determine the effects of structural features of the ribozyme on the reaction it catalyzes. Using this model, quantum chemical calculations must be performed to determine quantitatively the effects of structural features on catalysis. Previous studies of the reaction path have been conducted at the ab initio level, but these methods are limited to small models due to enormous computational requirements. Semiempirical methods have been applied to large systems in the past; however, the accuracy of these methods depends largely on a simple model of the ribozyme-catalyzed reaction, or hydrolysis of phosphoric acid. We find that the results are qualitatively similar to ab initio results using large basis sets. Therefore, PM3 is suitable for studying the reaction path of the ribozyme-catalyzed reaction.

A new network representation of the metabolism to detect chemical transformation modules.

PubMed

Sorokina, Maria; Medigue, Claudine; Vallenet, David

2015-11-14

Metabolism is generally modeled by directed networks where nodes represent reactions and/or metabolites. In order to explore metabolic pathway conservation and divergence among organisms, previous studies were based on graph alignment to find similar pathways. Few years ago, the concept of chemical transformation modules, also called reaction modules, was introduced and correspond to sequences of chemical transformations which are conserved in metabolism. We propose here a novel graph representation of the metabolic network where reactions sharing a same chemical transformation type are grouped in Reaction Molecular Signatures (RMS). RMS were automatically computed for all reactions and encode changes in atoms and bonds. A reaction network containing all available metabolic knowledge was then reduced by an aggregation of reaction nodes and edges to obtain a RMS network. Paths in this network were explored and a substantial number of conserved chemical transformation modules was detected. Furthermore, this graph-based formalism allows us to define several path scores reflecting different biological conservation meanings. These scores are significantly higher for paths corresponding to known metabolic pathways and were used conjointly to build association rules that should predict metabolic pathway types like biosynthesis or degradation. This representation of metabolism in a RMS network offers new insights to capture relevant metabolic contexts. Furthermore, along with genomic context methods, it should improve the detection of gene clusters corresponding to new metabolic pathways.

Energy aware path planning in complex four dimensional environments

NASA Astrophysics Data System (ADS)

Chakrabarty, Anjan

This dissertation addresses the problem of energy-aware path planning for small autonomous vehicles. While small autonomous vehicles can perform missions that are too risky (or infeasible) for larger vehicles, the missions are limited by the amount of energy that can be carried on board the vehicle. Path planning techniques that either minimize energy consumption or exploit energy available in the environment can thus increase range and endurance. Path planning is complicated by significant spatial (and potentially temporal) variations in the environment. While the main focus is on autonomous aircraft, this research also addresses autonomous ground vehicles. Range and endurance of small unmanned aerial vehicles (UAVs) can be greatly improved by utilizing energy from the atmosphere. Wind can be exploited to minimize energy consumption of a small UAV. But wind, like any other atmospheric component , is a space and time varying phenomenon. To effectively use wind for long range missions, both exploration and exploitation of wind is critical. This research presents a kinematics based tree algorithm which efficiently handles the four dimensional (three spatial and time) path planning problem. The Kinematic Tree algorithm provides a sequence of waypoints, airspeeds, heading and bank angle commands for each segment of the path. The planner is shown to be resolution complete and computationally efficient. Global optimality of the cost function cannot be claimed, as energy is gained from the atmosphere, making the cost function inadmissible. However the Kinematic Tree is shown to be optimal up to resolution if the cost function is admissible. Simulation results show the efficacy of this planning method for a glider in complex real wind data. Simulation results verify that the planner is able to extract energy from the atmosphere enabling long range missions. The Kinematic Tree planning framework, developed to minimize energy consumption of UAVs, is applied for path planning in ground robots. In traditional path planning problem the focus is on obstacle avoidance and navigation. The optimal Kinematic Tree algorithm named Kinematic Tree* is shown to find optimal paths to reach the destination while avoiding obstacles. A more challenging path planning scenario arises for planning in complex terrain. This research shows how the Kinematic Tree* algorithm can be extended to find minimum energy paths for a ground vehicle in difficult mountainous terrain.

Glycerol electro-oxidation on a carbon-supported platinum catalyst at intermediate temperatures

NASA Astrophysics Data System (ADS)

Ishiyama, Keisuke; Kosaka, Fumihiko; Shimada, Iori; Oshima, Yoshito; Otomo, Junichiro

2013-03-01

The electro-oxidation of glycerol on a carbon-supported platinum catalyst (Pt/C) in combination with a reaction products analysis was investigated at intermediate temperatures (235-260 °C) using a single cell with a CsH2PO4 proton conducting solid electrolyte. A high current density was achieved. The main products were H2, CO2 and CO but the formation of C2 compounds, such as glycolic acid and ethane, was also observed. In addition, several C3 compounds were detected as minor products. A reaction products analysis revealed that the C-C bond dissociation ratio of glycerol was 70-80% at both low and high potentials (>200 mV vs. reversible hydrogen electrode) at 250 °C, suggesting that rapid dissociation occurs on Pt/C. The reaction products analysis also suggested that hydrogen production via thermal decomposition and/or steam reforming of glycerol (indirect path) and direct electro-oxidation of glycerol (direct path) proceed in parallel. More detailed reaction paths involving C1, C2 and C3 reaction products are discussed as well as the possible rate-determining step in glycerol electro-oxidation at intermediate temperatures.

User's guide to PHREEQC, a computer program for speciation, reaction-path, advective-transport, and inverse geochemical calculations

USGS Publications Warehouse

Parkhurst, D.L.

1995-01-01

PHREEQC is a computer program written in the C pwgranuning language that is designed to perform a wide variety of aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations, (2) reaction-path and advective-transport calculations involving specified irreversible reactions, mixing of solutions, mineral and gas equilibria surface-complex-ation reactions, and ion-exchange reactions, and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for composition differences between waters, within specified compositional uncertainties. PHREEQC is derived from the Fortran program PHREEQE, but it has been completely rewritten in C with the addition many new capabilities. New features include the capabilities to use redox couples to distribute redox elements among their valence states in speciation calculations; to model ion-exchange and surface-compiexation reactions; to model reactions with a fixed-pressure, multicomponent gas phase (that is, a gas bubble); to calculate the mass of water in the aqueous phase during reaction and transport calculations; to keep track of the moles of minerals present in the solid phases and determine antomaticaHy the thermodynamically stable phase assemblage; to simulate advective transport in combination with PHREEQC's reaction-modeling capability; and to make inverse modeling calculations that allow for uncertainties in the analytical data. The user interface is improved through the use of a simplified approach to redox reactions, which includes explicit mole-balance equations for hydrogen and oxygen; the use of a revised input that is modular and completely free format; and the use of mineral names and standard chemical symbolism rather than index numbers. The use of (2 eliminates nearly all limitations on army sizes, including numbers of elements, aqueous species, solutions, phases, and lengths of character strings. A new equation solver that optimizes a set of equalities subject to both equality and inequality constraints is used to determine the thermodynamically stable set of phases in equilibrium with a solution. A more complete Newton-Raphson formulation, master-species switching, and scaling of the algebraic equations reduce the number of failures of the nunmrical method in PHREEQC relative to PHREEQE. This report presents the equations that are the basis for chemical equilibrium and inverse-modeling calculations in PHREEQC, describes the input for the program, and presents twelve examples that demonstrate most of the program's capabilities.

Optimal exploration systems

NASA Astrophysics Data System (ADS)

Klesh, Andrew T.

This dissertation studies optimal exploration, defined as the collection of information about given objects of interest by a mobile agent (the explorer) using imperfect sensors. The key aspects of exploration are kinematics (which determine how the explorer moves in response to steering commands), energetics (which determine how much energy is consumed by motion and maneuvers), informatics (which determine the rate at which information is collected) and estimation (which determines the states of the objects). These aspects are coupled by the steering decisions of the explorer. We seek to improve exploration by finding trade-offs amongst these couplings and the components of exploration: the Mission, the Path and the Agent. A comprehensive model of exploration is presented that, on one hand, accounts for these couplings and on the other hand is simple enough to allow analysis. This model is utilized to pose and solve several exploration problems where an objective function is to be minimized. Specific functions to be considered are the mission duration and the total energy. These exploration problems are formulated as optimal control problems and necessary conditions for optimality are obtained in the form of two-point boundary value problems. An analysis of these problems reveals characteristics of optimal exploration paths. Several regimes are identified for the optimal paths including the Watchtower, Solar and Drag regime, and several non-dimensional parameters are derived that determine the appropriate regime of travel. The so-called Power Ratio is shown to predict the qualitative features of the optimal paths, provide a metric to evaluate an aircrafts design and determine an aircrafts capability for flying perpetually. Optimal exploration system drivers are identified that provide perspective as to the importance of these various regimes of flight. A bank-to-turn solar-powered aircraft flying at constant altitude on Mars is used as a specific platform for analysis using the coupled model. Flight-paths found with this platform are presented that display the optimal exploration problem characteristics. These characteristics are used to form heuristics, such as a Generalized Traveling Salesman Problem solver, to simplify the exploration problem. These heuristics are used to empirically show the successful completion of an exploration mission by a physical explorer.

A theory-based dual-focus alcohol intervention for preadolescents: the Strong African American Families Program.

PubMed

Gerrard, Meg; Gibbons, Frederick X; Brody, Gene H; Murry, Velma McBride; Cleveland, Michael J; Wills, Thomas A

2006-06-01

This study examined mediators of the Strong African American Families Program, a randomized, dual-focus prevention trial intended to delay the onset of alcohol use and reduce alcohol consumption among rural African American youths. More specifically, it demonstrated that changes in consumption 2 yrs after the intervention were mediated through 2 different paths, a social reaction path and a reasoned/intention path. The social reaction path provided evidence that relative to the control condition, the intervention decreased children's willingness to drink by making their images of drinkers less favorable. The reasoned/intention path provided evidence that the intervention influenced the children's intentions to drink by increasing targeted parenting behaviors related to alcohol. Furthermore, the data demonstrate that these changes in willingness and intentions were independently associated with alcohol consumption at the follow-up, and they suggest that a dual-process model approach that targets both intentions and willingness can be more successful than either approach alone.

Vehicle path-planning in three dimensions using optics analogs for optimizing visibility and energy cost

NASA Technical Reports Server (NTRS)

Rowe, Neil C.; Lewis, David H.

1989-01-01

Path planning is an important issue for space robotics. Finding safe and energy-efficient paths in the presence of obstacles and other constraints can be complex although important. High-level (large-scale) path planning for robotic vehicles was investigated in three-dimensional space with obstacles, accounting for: (1) energy costs proportional to path length; (2) turn costs where paths change trajectory abruptly; and (3) safety costs for the danger associated with traversing a particular path due to visibility or invisibility from a fixed set of observers. Paths optimal with respect to these cost factors are found. Autonomous or semi-autonomous vehicles were considered operating either in a space environment around satellites and space platforms, or aircraft, spacecraft, or smart missiles operating just above lunar and planetary surfaces. One class of applications concerns minimizing detection, as for example determining the best way to make complex modifications to a satellite without being observed by hostile sensors; another example is verifying there are no paths (holes) through a space defense system. Another class of applications concerns maximizing detection, as finding a good trajectory between mountain ranges of a planet while staying reasonably close to the surface, or finding paths for a flight between two locations that maximize the average number of triangulation points available at any time along the path.

Grey-Theory-Based Optimization Model of Emergency Logistics Considering Time Uncertainty.

PubMed

Qiu, Bao-Jian; Zhang, Jiang-Hua; Qi, Yuan-Tao; Liu, Yang

2015-01-01

Natural disasters occur frequently in recent years, causing huge casualties and property losses. Nowadays, people pay more and more attention to the emergency logistics problems. This paper studies the emergency logistics problem with multi-center, multi-commodity, and single-affected-point. Considering that the path near the disaster point may be damaged, the information of the state of the paths is not complete, and the travel time is uncertainty, we establish the nonlinear programming model that objective function is the maximization of time-satisfaction degree. To overcome these drawbacks: the incomplete information and uncertain time, this paper firstly evaluates the multiple roads of transportation network based on grey theory and selects the reliable and optimal path. Then simplify the original model under the scenario that the vehicle only follows the optimal path from the emergency logistics center to the affected point, and use Lingo software to solve it. The numerical experiments are presented to show the feasibility and effectiveness of the proposed method.

Grey-Theory-Based Optimization Model of Emergency Logistics Considering Time Uncertainty

PubMed Central

Qiu, Bao-Jian; Zhang, Jiang-Hua; Qi, Yuan-Tao; Liu, Yang

2015-01-01

Natural disasters occur frequently in recent years, causing huge casualties and property losses. Nowadays, people pay more and more attention to the emergency logistics problems. This paper studies the emergency logistics problem with multi-center, multi-commodity, and single-affected-point. Considering that the path near the disaster point may be damaged, the information of the state of the paths is not complete, and the travel time is uncertainty, we establish the nonlinear programming model that objective function is the maximization of time-satisfaction degree. To overcome these drawbacks: the incomplete information and uncertain time, this paper firstly evaluates the multiple roads of transportation network based on grey theory and selects the reliable and optimal path. Then simplify the original model under the scenario that the vehicle only follows the optimal path from the emergency logistics center to the affected point, and use Lingo software to solve it. The numerical experiments are presented to show the feasibility and effectiveness of the proposed method. PMID:26417946

Cheap but accurate calculation of chemical reaction rate constants from ab initio data, via system-specific, black-box force fields

NASA Astrophysics Data System (ADS)

Steffen, Julien; Hartke, Bernd

2017-10-01

Building on the recently published quantum-mechanically derived force field (QMDFF) and its empirical valence bond extension, EVB-QMDFF, it is now possible to generate a reliable potential energy surface for any given elementary reaction step in an essentially black box manner. This requires a limited and pre-defined set of reference data near the reaction path and generates an accurate approximation of the reference potential energy surface, on and off the reaction path. This intermediate representation can be used to generate reaction rate data, with far better accuracy and reliability than with traditional approaches based on transition state theory (TST) or variational extensions thereof (VTST), even if those include sophisticated tunneling corrections. However, the additional expense at the reference level remains very modest. We demonstrate all this for three arbitrarily chosen example reactions.

Comparison of some evolutionary algorithms for optimization of the path synthesis problem

NASA Astrophysics Data System (ADS)

Grabski, Jakub Krzysztof; Walczak, Tomasz; Buśkiewicz, Jacek; Michałowska, Martyna

2018-01-01

The paper presents comparison of the results obtained in a mechanism synthesis by means of some selected evolutionary algorithms. The optimization problem considered in the paper as an example is the dimensional synthesis of the path generating four-bar mechanism. In order to solve this problem, three different artificial intelligence algorithms are employed in this study.

Study of Double-Weighted Graph Model and Optimal Path Planning for Tourist Scenic Area Oriented Intelligent Tour Guide

NASA Astrophysics Data System (ADS)

Shi, Y.; Long, Y.; Wi, X. L.

2014-04-01

When tourists visiting multiple tourist scenic spots, the travel line is usually the most effective road network according to the actual tour process, and maybe the travel line is different from planned travel line. For in the field of navigation, a proposed travel line is normally generated automatically by path planning algorithm, considering the scenic spots' positions and road networks. But when a scenic spot have a certain area and have multiple entrances or exits, the traditional described mechanism of single point coordinates is difficult to reflect these own structural features. In order to solve this problem, this paper focuses on the influence on the process of path planning caused by scenic spots' own structural features such as multiple entrances or exits, and then proposes a doubleweighted Graph Model, for the weight of both vertexes and edges of proposed Model can be selected dynamically. And then discusses the model building method, and the optimal path planning algorithm based on Dijkstra algorithm and Prim algorithm. Experimental results show that the optimal planned travel line derived from the proposed model and algorithm is more reasonable, and the travelling order and distance would be further optimized.

Reaction chemistry in rechargeable Li-O2 batteries.

PubMed

Lim, Hee-Dae; Lee, Byungju; Bae, Youngjoon; Park, Hyeokjun; Ko, Youngmin; Kim, Haegyeom; Kim, Jinsoo; Kang, Kisuk

2017-05-22

The seemingly simple reaction of Li-O 2 batteries involving lithium and oxygen makes this chemistry attractive for high-energy-density storage systems; however, achieving this reaction in practical rechargeable Li-O 2 batteries has proven difficult. The reaction paths leading to the final Li 2 O 2 discharge products can be greatly affected by the operating conditions or environment, which often results in major side reactions. Recent research findings have begun to reveal how the reaction paths may be affected by the surrounding conditions and to uncover the factors contributing to the difficulty in achieving the reactions of lithium and oxygen. This progress report describes the current state of understanding of the electrode reaction mechanisms in Li-O 2 batteries; the factors that affect reaction pathways; and the effect of cell components such as solvents, salts, additives, and catalysts on the discharge product and its decomposition during charging. This comprehensive review of the recent progress in understanding the reaction chemistry of the Li-O 2 system will serve as guidelines for future research and aid in the development of reliable high-energy-density rechargeable Li-O 2 batteries.

Aircraft path planning for optimal imaging using dynamic cost functions

NASA Astrophysics Data System (ADS)

Christie, Gordon; Chaudhry, Haseeb; Kochersberger, Kevin

2015-05-01

Unmanned aircraft development has accelerated with recent technological improvements in sensing and communications, which has resulted in an "applications lag" for how these aircraft can best be utilized. The aircraft are becoming smaller, more maneuverable and have longer endurance to perform sensing and sampling missions, but operating them aggressively to exploit these capabilities has not been a primary focus in unmanned systems development. This paper addresses a means of aerial vehicle path planning to provide a realistic optimal path in acquiring imagery for structure from motion (SfM) reconstructions and performing radiation surveys. This method will allow SfM reconstructions to occur accurately and with minimal flight time so that the reconstructions can be executed efficiently. An assumption is made that we have 3D point cloud data available prior to the flight. A discrete set of scan lines are proposed for the given area that are scored based on visibility of the scene. Our approach finds a time-efficient path and calculates trajectories between scan lines and over obstacles encountered along those scan lines. Aircraft dynamics are incorporated into the path planning algorithm as dynamic cost functions to create optimal imaging paths in minimum time. Simulations of the path planning algorithm are shown for an urban environment. We also present our approach for image-based terrain mapping, which is able to efficiently perform a 3D reconstruction of a large area without the use of GPS data.

Hierarchical heuristic search using a Gaussian mixture model for UAV coverage planning.

PubMed

Lin, Lanny; Goodrich, Michael A

2014-12-01

During unmanned aerial vehicle (UAV) search missions, efficient use of UAV flight time requires flight paths that maximize the probability of finding the desired subject. The probability of detecting the desired subject based on UAV sensor information can vary in different search areas due to environment elements like varying vegetation density or lighting conditions, making it likely that the UAV can only partially detect the subject. This adds another dimension of complexity to the already difficult (NP-Hard) problem of finding an optimal search path. We present a new class of algorithms that account for partial detection in the form of a task difficulty map and produce paths that approximate the payoff of optimal solutions. The algorithms use the mode goodness ratio heuristic that uses a Gaussian mixture model to prioritize search subregions. The algorithms search for effective paths through the parameter space at different levels of resolution. We compare the performance of the new algorithms against two published algorithms (Bourgault's algorithm and LHC-GW-CONV algorithm) in simulated searches with three real search and rescue scenarios, and show that the new algorithms outperform existing algorithms significantly and can yield efficient paths that yield payoffs near the optimal.

Integrated optimization of unmanned aerial vehicle task allocation and path planning under steady wind.

PubMed

Luo, He; Liang, Zhengzheng; Zhu, Moning; Hu, Xiaoxuan; Wang, Guoqiang

2018-01-01

Wind has a significant effect on the control of fixed-wing unmanned aerial vehicles (UAVs), resulting in changes in their ground speed and direction, which has an important influence on the results of integrated optimization of UAV task allocation and path planning. The objective of this integrated optimization problem changes from minimizing flight distance to minimizing flight time. In this study, the Euclidean distance between any two targets is expanded to the Dubins path length, considering the minimum turning radius of fixed-wing UAVs. According to the vector relationship between wind speed, UAV airspeed, and UAV ground speed, a method is proposed to calculate the flight time of UAV between targets. On this basis, a variable-speed Dubins path vehicle routing problem (VS-DP-VRP) model is established with the purpose of minimizing the time required for UAVs to visit all the targets and return to the starting point. By designing a crossover operator and mutation operator, the genetic algorithm is used to solve the model, the results of which show that an effective UAV task allocation and path planning solution under steady wind can be provided.

Integrated optimization of unmanned aerial vehicle task allocation and path planning under steady wind

PubMed Central

Liang, Zhengzheng; Zhu, Moning; Hu, Xiaoxuan; Wang, Guoqiang

2018-01-01

Wind has a significant effect on the control of fixed-wing unmanned aerial vehicles (UAVs), resulting in changes in their ground speed and direction, which has an important influence on the results of integrated optimization of UAV task allocation and path planning. The objective of this integrated optimization problem changes from minimizing flight distance to minimizing flight time. In this study, the Euclidean distance between any two targets is expanded to the Dubins path length, considering the minimum turning radius of fixed-wing UAVs. According to the vector relationship between wind speed, UAV airspeed, and UAV ground speed, a method is proposed to calculate the flight time of UAV between targets. On this basis, a variable-speed Dubins path vehicle routing problem (VS-DP-VRP) model is established with the purpose of minimizing the time required for UAVs to visit all the targets and return to the starting point. By designing a crossover operator and mutation operator, the genetic algorithm is used to solve the model, the results of which show that an effective UAV task allocation and path planning solution under steady wind can be provided. PMID:29561888

Influences of Temperature and Metal on Subcritical Hydrothermal Liquefaction of Hyperaccumulator: Implications for the Recycling of Hazardous Hyperaccumulators.

PubMed

Qian, Feng; Zhu, Xiangdong; Liu, Yuchen; Shi, Quan; Wu, Longhua; Zhang, Shicheng; Chen, Jianmin; Ren, Zhiyong Jason

2018-02-20

Waste Sedum plumbizincicola, a zinc (Zn) hyperaccumulator during phytoremediation, was recycled via a subcritical hydrothermal liquefaction (HTL) reaction into multiple streams of products, including hydrochar, bio-oil, and carboxylic acids. Results show approximately 90% of Zn was released from the S. plumbizincicola biomass during HTL at an optimized temperature of 220 °C, and the release risk was mitigated via HTL reaction for hydrochar production. The low-Zn hydrochar (∼200 mg/kg compared to original plant of 1558 mg/kg) was further upgraded into porous carbon (PC) with high porosity (930 m 2 /g) and excellent capability of carbon dioxide (CO 2 ) capture (3 mmol/g). The porosity, micropore structure, and graphitization degree of PCs were manipulated by the thermal recalcitrance of hydrochar. More importantly, results showed that the released Zn 2+ could effectively promote the production of acetic acid via the oxidation of furfural (FF) and 5-(hydroxymethyl)-furfural (HMF). Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with negative electrospray ionization analysis confirmed the deoxygenation and depolymerization reactions and the production of long chain fatty acids during HTL reaction of S. plumbizincicola. This work provides a new path for the recycling of waste hyperaccumulator biomass into value-added products.

Theoretical Proposal for the Whole Phosphate Diester Hydrolysis Mechanism Promoted by a Catalytic Promiscuous Dinuclear Copper(II) Complex.

PubMed

Esteves, Lucas F; Rey, Nicolás A; Dos Santos, Hélio F; Costa, Luiz Antônio S

2016-03-21

The catalytic mechanism that involves the cleavage of the phosphate diester model BDNPP (bis(2,4-dinitrophenyl) phosphate) catalyzed through a dinuclear copper complex is investigated in the current study. The metal complex was originally designed to catalyze catechol oxidation, and it showed an interesting catalytic promiscuity case in biomimetic systems. The current study investigates two different reaction mechanisms through quantum mechanics calculations in the gas phase, and it also includes the solvent effect through PCM (polarizable continuum model) single-point calculations using water as solvent. Two mechanisms are presented in order to fully describe the phosphate diester hydrolysis. Mechanism 1 is of the S(N)2 type, which involves the direct attack of the μ-OH bridge between the two copper(II) ions toward the phosphorus center, whereas mechanism 2 is the process in which hydrolysis takes place through proton transfer between the oxygen atom in the bridging hydroxo ligand and the other oxygen atom in the phosphate model. Actually, the present theoretical study shows two possible reaction paths in mechanism 1. Its first reaction path (p1) involves a proton transfer that occurs immediately after the hydrolytic cleavage, so that the proton transfer is the rate-determining step, which is followed by the entry of two water molecules. Its second reaction path (p2) consists of the entry of two water molecules right after the hydrolytic cleavage, but with no proton transfer; thus, hydrolytic cleavage is the rate-limiting step. The most likely catalytic path occurs in mechanism 1, following the second reaction path (p2), since it involves the lowest free energy activation barrier (ΔG(⧧) = 23.7 kcal mol(-1), in aqueous solution). A kinetic analysis showed that the experimental k(obs) value of 1.7 × 10(-5) s(-1) agrees with the calculated value k1 = 2.6 × 10(-5) s(-1); the concerted mechanism is kinetically favorable. The KIE (kinetic isotope effect) analysis applied to the second reaction path (p2) in mechanism 1 was also taken into account to assess the changes that take place in TS1-i (transition state of mechanism 1) and to perfectly characterize the mechanism described herein.

Quantum optimal control pathways of ozone isomerization dynamics subject to competing dissociation: A two-state one-dimensional model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kurosaki, Yuzuru, E-mail: kurosaki.yuzuru@jaea.go.jp; Ho, Tak-San, E-mail: tsho@Princeton.EDU; Rabitz, Herschel, E-mail: hrabitz@Princeton.EDU

We construct a two-state one-dimensional reaction-path model for ozone open → cyclic isomerization dynamics. The model is based on the intrinsic reaction coordinate connecting the cyclic and open isomers with the O{sub 2} + O asymptote on the ground-state {sup 1}A{sup ′} potential energy surface obtained with the high-level ab initio method. Using this two-state model time-dependent wave packet optimal control simulations are carried out. Two possible pathways are identified along with their respective band-limited optimal control fields; for pathway 1 the wave packet initially associated with the open isomer is first pumped into a shallow well on the excitedmore » electronic state potential curve and then driven back to the ground electronic state to form the cyclic isomer, whereas for pathway 2 the corresponding wave packet is excited directly to the primary well of the excited state potential curve. The simulations reveal that the optimal field for pathway 1 produces a final yield of nearly 100% with substantially smaller intensity than that obtained in a previous study [Y. Kurosaki, M. Artamonov, T.-S. Ho, and H. Rabitz, J. Chem. Phys. 131, 044306 (2009)] using a single-state one-dimensional model. Pathway 2, due to its strong coupling to the dissociation channel, is less effective than pathway 1. The simulations also show that nonlinear field effects due to molecular polarizability and hyperpolarizability are small for pathway 1 but could become significant for pathway 2 because much higher field intensity is involved in the latter. The results suggest that a practical control may be feasible with the aid of a few lowly excited electronic states for ozone isomerization.« less

Characterization of the Minimum Energy Paths and Energetics for the Reaction of Vinylidene with Acetylene

NASA Technical Reports Server (NTRS)

Walch, Stephen P.; Taylor, Peter R.

1995-01-01

The reaction of vinylidene (CH2C) with acetylene may be an initiating reaction in soot formation. We report minimum energy paths and accurate energetics for a pathway leading to vinyl-acetylene and for a number of isomers of C4H4. The calculations use complete active space self-consistent field (CASSCF) derivative methods to characterize the stationary points and internally contacted configuration interaction (ICCI) and/or coupled cluster singles and doubles with a perturbational estimate of triple excitations (CCSD(T)) to determine the energetics. We find an entrance channel barrier of about 5 kcal/mol for the addition of vinylidene to acetylene, but no barriers above reactants for the reaction pathway leading to vinyl-acetylene.

Characterization of the Minimum Energy Paths and Energetics for the reaction of Vinylidene with Acetylene

NASA Technical Reports Server (NTRS)

Walch, Stephen P.; Taylor, Peter R.

1995-01-01

The reaction of vinylidene (CH2C) with acetylene may be an initiating reaction in soot formation. We report minimum energy paths and accurate energetics for a pathway leading to vinylacetylene and for a number of isomers Of C4H4. The calculations use complete active space self-consistent field (CASSCF) derivative methods to characterize the stationary points and internally contacted configuration interaction (ICCI) and/or coupled cluster singles and doubles with a perturbational estimate of triple excitations (CCSD(T)) to determine the energetics. We find an entrance channel barrier of about 5 kcal/mol for the addition of vinylidene to acetylene, but no barriers above reactants for the reaction pathway leading to vinylacetylene.

a Walking Disturbance Index Suggestions for Optimized Path Search for the People with Reduced Mobility

NASA Astrophysics Data System (ADS)

Moon, M.; Bang, Y.; Yu, K.; Kim, J.

2015-10-01

Recently, due to the increased penetration of smart devices and the development of geographic information system (GIS) technology, various route guidance services for pedestrians have been developed. However, until now, pedestrian navigation services for the people with reduced mobility (people who experience discomfort in transportation) including wheelchair users, the elderly, and pregnant women have not been provided. In this study, we present a walking disturbance index methodology for searching an optimized path for the people with reduced mobility by defining the factors that affect the walking of the people with reduced mobility and deriving the weights of these factors. In future research, we expect to be able to provide a navigation system that gives an optimized path for the people with reduced mobility using this method.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schachtl, Eva; Yoo, Jong Suk; Gutiérrez, Oliver Y.

The reaction network and elementary steps of the hydrogenation of phenanthrene are explored on parent and Ni-promoted MoS2/c-Al2O3. Two pathways were identified, i.e., Path 1: Phenanthrene _ 9,10-dihydrophenanthrene (DiHPhe)?1,2,3,4,4a,9,10,10a-octahydro-phenanthrene (asymOHPhe), and Path 2: Phenanthrene ?1,2,3,4-tetrahydrophenanthrene (TetHPhe)?1,2,3,4,5,6,7,8-octahydrophenan threne. The steps TetHPhe?asymOHPhe (hydrogenation), and DiHPhe?TetHPhe (hydrogenationisomerization) become notable at phenanthrene conversions above 20%. The reaction preferentially proceeds via Path 1 (90% selectivity) on MoS2/Al2O3. Ni promotion (Ni/(Ni + Mo) molar ratio of 0.3 at the edges on MoS2) increases the hydrogenation activity per active edge twofold and leads to 50% selectivity to both pathways. The reaction orders in H2 vary from _0.8more » on MoS2/Al2O3 to _1.2 on Ni-MoS2/Al2O3, whereas the reaction orders in phenanthrene (_0.6) hardly depend on Ni promotion. The reaction orders in H2S are zero on MoS2/Al2O3 and slightly negative on Ni-MoS2/Al2O3. DFT calculations indicate that phenanthrene is preferentially adsorbed parallel to the basal planes, while H is located at the edges perpendicular to the basal planes. Theory also suggests that Ni atoms, incorporated preferentially on the S-edges, increase the stability of hydrogenated intermediates. Hydrogenation of phenanthrene proceeds through quasi-equilibrated adsorption of the reactants followed by consecutive addition of hydrogen pairs to the adsorbed hydrocarbon. The rate determining steps for the formation of DiHPhe and TetHPhe are the addition of the first and second hydrogen pair, respectively. The concentration of SH groups (activated H at the edges) increases with Ni promotion linearly correlating the rates of Path 1 and Path 2, albeit with different functions. The enhancing effect of Ni on Path 2 is attributed to accelerated hydrogen addition to adsorbed hydrocarbons without important changes in their coverages.« less

Patients' expectations of the role of the community pharmacist: Development and testing of a conceptual model.

PubMed

Sabater-Galindo, Marta; Ruiz de Maya, Salvador; Benrimoj, Shalom I; Gastelurrutia, Miguel Angel; Martínez-Martínez, Fernando; Sabater-Hernández, Daniel

The roles of community pharmacists are evolving to include provision of expanded professional pharmacy services, thus leading to an increased interest in pharmacist-patient interactions. Role theory can be used to explain the interaction between this pair of individuals, by focusing on the roles performed by each one. To develop and test a model that relates patients' image of the pharmacist to their expectations of pharmacist's role, and how this then influences patients' reactions toward the pharmacist's role. A qualitative study was undertaken, and a questionnaire was created for the development of the model, based on role theory. The content, dimensions, validity and reliability of the questionnaire were pre-tested qualitatively and in a pilot mail survey. The reliability and validity of the proposed model were tested using confirmatory factor analysis (CFA). Structural equation modelling (SEM) was used to explain relationships between dimensions of the final model. A final model was developed. CFA concluded that the model was valid and reliable (Goodness of Fit indices: χ 2 (109) = 227.662, P = 0.000, RMSEA = 0.05, SRMR = 0.05, GFI = 1.00, NNFI = 0.90, CFI = 0.92). SEM indicated that "perceived pharmacist image" was associated positively and significantly with both "professional expectations" (the standardized path coefficient of (H) = 0.719, P < 0.05), as well as "courtesy expectations" (the standardized path coefficient of (H) = 0.582, P < 0.05). At the same time, "professional expectations" were associated positively and significantly with "positive reactions" (the standardized path coefficient of (H) = 0.358, P < 0.05), but negatively with "Negative reactions" (the standardized path coefficient of (H) = -0.427, P < 0.05). "Courtesy expectations" were associated positively and significantly with "positive reactions" (the standardized path coefficient of (H) = 0.081, P < 0.05), as well as "negative reactions" (the standardized path coefficient of (H) = 0.450, P < 0.05). A valid and reliable model of patients' image of the pharmacist related to their expectations and reactions to the pharmacist's role was developed and tested. When the perceived image of the pharmacist is enhanced, patients' expectations of the pharmacist are heightened; in turn, these expectations were associated with reactions of patients. Copyright © 2016 Elsevier Inc. All rights reserved.

System and method for optimal load and source scheduling in context aware homes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shetty, Pradeep; Foslien Graber, Wendy; Mangsuli, Purnaprajna R.

A controller for controlling energy consumption in a home includes a constraints engine to define variables for multiple appliances in the home corresponding to various home modes and persona of an occupant of the home. A modeling engine models multiple paths of energy utilization of the multiple appliances to place the home into a desired state from a current context. An optimal scheduler receives the multiple paths of energy utilization and generates a schedule as a function of the multiple paths and a selected persona to place the home in a desired state.

A Detailed Chemical Kinetic Model for TNT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pitz, W J; Westbrook, C K

2005-01-13

A detailed chemical kinetic mechanism for 2,4,6-tri-nitrotoluene (TNT) has been developed to explore problems of explosive performance and soot formation during the destruction of munitions. The TNT mechanism treats only gas-phase reactions. Reactions for the decomposition of TNT and for the consumption of intermediate products formed from TNT are assembled based on information from the literature and on current understanding of aromatic chemistry. Thermodynamic properties of intermediate and radical species are estimated by group additivity. Reaction paths are developed based on similar paths for aromatic hydrocarbons. Reaction-rate constant expressions are estimated from the literature and from analogous reactions where themore » rate constants are available. The detailed reaction mechanism for TNT is added to existing reaction mechanisms for RDX and for hydrocarbons. Computed results show the effect of oxygen concentration on the amount of soot precursors that are formed in the combustion of RDX and TNT mixtures in N{sub 2}/O{sub 2} mixtures.« less

Multicomponent Density Functional Theory: Impact of Nuclear Quantum Effects on Proton Affinities and Geometries.

PubMed

Brorsen, Kurt R; Yang, Yang; Hammes-Schiffer, Sharon

2017-08-03

Nuclear quantum effects such as zero point energy play a critical role in computational chemistry and often are included as energetic corrections following geometry optimizations. The nuclear-electronic orbital (NEO) multicomponent density functional theory (DFT) method treats select nuclei, typically protons, quantum mechanically on the same level as the electrons. Electron-proton correlation is highly significant, and inadequate treatments lead to highly overlocalized nuclear densities. A recently developed electron-proton correlation functional, epc17, has been shown to provide accurate nuclear densities for molecular systems. Herein, the NEO-DFT/epc17 method is used to compute the proton affinities for a set of molecules and to examine the role of nuclear quantum effects on the equilibrium geometry of FHF - . The agreement of the computed results with experimental and benchmark values demonstrates the promise of this approach for including nuclear quantum effects in calculations of proton affinities, pK a 's, optimized geometries, and reaction paths.

UCAV path planning in the presence of radar-guided surface-to-air missile threats

NASA Astrophysics Data System (ADS)

Zeitz, Frederick H., III

This dissertation addresses the problem of path planning for unmanned combat aerial vehicles (UCAVs) in the presence of radar-guided surface-to-air missiles (SAMs). The radars, collocated with SAM launch sites, operate within the structure of an Integrated Air Defense System (IADS) that permits communication and cooperation between individual radars. The problem is formulated in the framework of the interaction between three sub-systems: the aircraft, the IADS, and the missile. The main features of this integrated model are: The aircraft radar cross section (RCS) depends explicitly on both the aspect and bank angles; hence, the RCS and aircraft dynamics are coupled. The probabilistic nature of IADS tracking is accounted for; namely, the probability that the aircraft has been continuously tracked by the IADS depends on the aircraft RCS and range from the perspective of each radar within the IADS. Finally, the requirement to maintain tracking prior to missile launch and during missile flyout are also modeled. Based on this model, the problem of UCAV path planning is formulated as a minimax optimal control problem, with the aircraft bank angle serving as control. Necessary conditions of optimality for this minimax problem are derived. Based on these necessary conditions, properties of the optimal paths are derived. These properties are used to discretize the dynamic optimization problem into a finite-dimensional, nonlinear programming problem that can be solved numerically. Properties of the optimal paths are also used to initialize the numerical procedure. A homotopy method is proposed to solve the finite-dimensional, nonlinear programming problem, and a heuristic method is proposed to improve the discretization during the homotopy process. Based upon the properties of numerical solutions, a method is proposed for parameterizing and storing information for later recall in flight to permit rapid replanning in response to changing threats. Illustrative examples are presented that confirm the standard flying tactics of "denying range, aspect, and aim," by yielding flight paths that "weave" to avoid long exposures of aspects with large RCS.

An Application of Multi-Criteria Shortest Path to a Customizable Hex-Map Environment

DTIC Science & Technology

2015-03-26

forces which could act as intermediate destinations or obstacles to movement through the network. This is similar to a traveling salesman problem ...118 Abstract The shortest path problem of finding the optimal path through a complex network is well-studied in the field of operations research. This...research presents an applica- tion of the shortest path problem to a customizable map with terrain features and enemy engagement risk. The PathFinder

Neuromorphic transistor achieved by redox reaction of WO3 thin film

NASA Astrophysics Data System (ADS)

Tsuchiya, Takashi; Jayabalan, Manikandan; Kawamura, Kinya; Takayanagi, Makoto; Higuchi, Tohru; Jayavel, Ramasamy; Terabe, Kazuya

2018-04-01

An all-solid-state neuromorphic transistor composed of a WO3 thin film and a proton-conducting electrolyte was fabricated for application to next-generation information and communication technology including artificial neural networks. The drain current exhibited a 4-order-of-magnitude increment by redox reaction of the WO3 thin film owing to proton migration. Learning and forgetting characteristics were well tuned by the gate control of WO3 redox reactions owing to the separation of the current reading path and pulse application path in the transistor structure. This technique should lead to the development of versatile and low-power-consumption neuromorphic devices.

HCN and chromophore formation on Jupiter

NASA Technical Reports Server (NTRS)

Ferris, James P.; Ishikawa, Yoji

1987-01-01

Reaction paths for the formation of HCN and chromophores on Jupiter are suggested. The reactions involve photolysis of ammonia/acetylene mixtures. Experimental data supporting these pathways are reported.

Liouville action as path-integral complexity: from continuous tensor networks to AdS/CFT

NASA Astrophysics Data System (ADS)

Caputa, Pawel; Kundu, Nilay; Miyaji, Masamichi; Takayanagi, Tadashi; Watanabe, Kento

2017-11-01

We propose an optimization procedure for Euclidean path-integrals that evaluate CFT wave functionals in arbitrary dimensions. The optimization is performed by minimizing certain functional, which can be interpreted as a measure of computational complexity, with respect to background metrics for the path-integrals. In two dimensional CFTs, this functional is given by the Liouville action. We also formulate the optimization for higher dimensional CFTs and, in various examples, find that the optimized hyperbolic metrics coincide with the time slices of expected gravity duals. Moreover, if we optimize a reduced density matrix, the geometry becomes two copies of the entanglement wedge and reproduces the holographic entanglement entropy. Our approach resembles a continuous tensor network renormalization and provides a concrete realization of the proposed interpretation of AdS/CFT as tensor networks. The present paper is an extended version of our earlier report arXiv:1703.00456 and includes many new results such as evaluations of complexity functionals, energy stress tensor, higher dimensional extensions and time evolutions of thermofield double states.

Effect of enhanced manganese oxidation in the hyporheic zone on basin-scale geochemical mass balance

USGS Publications Warehouse

Harvey, Judson W.; Fuller, Christopher C.

1998-01-01

We determined the role of the hyporheic zone (the subsurface zone where stream water and shallow groundwater mix) in enhancing microbially mediated oxidation of dissolved manganese (to form manganese precipitates) in a drainage basin contaminated by copper mining. The fate of manganese is of overall importance to water quality in Pinal Creek Basin, Arizona, because manganese reactions affect the transport of trace metals. The basin-scale role of the hyporheic zone is difficult to quantify because stream-tracer studies do not always reliably characterize the cumulative effects of the hyporheic zone. This study determined cumulative effects of hyporheic reactions in Pinal Creek basin by characterizing manganese uptake at several spatial scales (stream-reach scale, hyporheic-flow-path scale, and sediment-grain scale). At the stream-reach scale a one-dimensional stream-transport model (including storage zones to represent hyporheic flow paths) was used to determine a reach-averaged time constant for manganese uptake in hyporheic zones, 1/λs, of 1.3 hours, which was somewhat faster but still similar to manganese uptake time constants that were measured directly in centimeter-scale hyporheic flow paths (1/λh= 2.6 hours), and in laboratory batch experiments using streambed sediment (1/λ = 2.7 hours). The modeled depths of subsurface storage zones (ds = 4–17 cm) and modeled residence times of water in storage zones (ts = 3–12 min) were both consistent with direct measurements in hyporheic flow paths (dh = 0–15 cm, th = 1–25 min). There was also good agreement between reach-scale modeling and direct measurements of the percentage removal of dissolved manganese in hyporheic flow paths (fs = 8.9%, andfh = 9.3%rpar;. Manganese uptake experiments in the laboratory using sediment from Pinal Creek demonstrated (through comparison of poisoned and unpoisoned treatments) that the manganese removal process was enhanced by microbially mediated oxidation. The cumulative effect of hyporheic exchange in Pinal Creek basin was to remove approximately 20% of the dissolved manganese flowing out of the drainage basin. Our results illustrate that the cumulative significance of reactive uptake in the hyporheic zone depends on the balance between chemical reaction rates, hyporheic porewater residence time, and turnover of streamflow through hyporheic flow paths. The similarity between the hyporheic reaction timescale (1/λs ≈ 1.3 hours), and the hyporheic porewater residence timescale (ts ≈ 8 min) ensured that there was adequate time for the reaction to progress. Furthermore, it was the similarity between the turnover length for stream water flow through hyporheic flow paths (Ls = stream velocity/storage-zone exchange coefficient ≈ 1.3 km) and the length of Pinal Creek (L ≈ 7 km), which ensured that all stream water passed through hyporheic flow paths several times. As a means to generalize our findings to other sites where similar types of hydrologic and chemical information are available, we suggest a cumulative significance index for hyporheic reactions, Rs = λstsL/Ls (dimensionless); higher values indicate a greater potential for hyporheic reactions to influence geochemical mass balance. Our experience in Pinal Creek basin suggests that values of Rs > 0.2 characterize systems where hyporheic reactions are likely to influence geochemical mass balance at the drainage-basin scale.

Theoretical study on stabilization mechanisms of nitrate esters using aromatic amines as stabilizers.

PubMed

Sun, Zhi-Dan; Fu, Xiao-Long; Yu, Hong-Jian; Fan, Xue-Zhong; Ju, Xue-Hai

2017-10-05

The propellants of nitrate esters can be stabilized by some aromatic amines practically. To probe the mechanism of this phenomenon, we performed DFT calculations on: (1) The decompositions of nitrate esters (with and without the catalysis of NO 2 ) and (2) the reaction between the stabilizers and the nitro dioxide (NO 2 is released during the storage of nitrate esters). The structures on the reaction paths (reactants, intermediates and products) were optimized at the (U)B3LYP/6-31G** level. It was shown that NO 2 lowers the activation energy barrier in the decomposition of nitrate ester by 11.82-17.86kJ/mol and efficiently catalyzes the rupture of ONO 2 bond. However, the aromatic amines, typical stabilizers for nitrate esters, can easily eliminate NO 2 with activation barriers as low as 27-113kJ/mol (with one exception of 128kJ/mol). These values are, for most cases, lower or much lower than the activation energy barriers for reactions between nitrate esters and NO 2 (127-137kJ/mol). Consequently, the stabilizers can block the NO 2 catalysis for the decompositions of nitrate esters. Copyright © 2017 Elsevier B.V. All rights reserved.

Understanding the physics and chemistry of reaction mechanisms from atomic contributions: a reaction force perspective.

PubMed

Vöhringer-Martinez, Esteban; Toro-Labbé, Alejandro

2012-07-12

Studying chemical reactions involves the knowledge of the reaction mechanism. Despite activation barriers describing the kinetics or reaction energies reflecting thermodynamic aspects, identifying the underlying physics and chemistry along the reaction path contributes essentially to the overall understanding of reaction mechanisms, especially for catalysis. In the past years the reaction force has evolved as a valuable tool to discern between structural changes and electrons' rearrangement in chemical reactions. It provides a framework to analyze chemical reactions and additionally a rational partition of activation and reaction energies. Here, we propose to separate these energies further in atomic contributions, which will shed new insights in the underlying reaction mechanism. As first case studies we analyze two intramolecular proton transfer reactions. Despite the atom based separation of activation barriers and reaction energies, we also assign the participation of each atom in structural changes or electrons' rearrangement along the intrinsic reaction coordinate. These participations allow us to identify the role of each atom in the two reactions and therfore the underlying chemistry. The knowledge of the reaction chemistry immediately leads us to suggest replacements with other atom types that would facilitate certain processes in the reaction. The characterization of the contribution of each atom to the reaction energetics, additionally, identifies the reactive center of a molecular system that unites the main atoms contributing to the potential energy change along the reaction path.

Assessment of Masonry Buildings Subjected to Landslide-Induced Settlements: From Load Path Method to Evolutionary Optimization Method

NASA Astrophysics Data System (ADS)

Palmisano, Fabrizio; Elia, Angelo

2017-10-01

One of the main difficulties, when dealing with landslide structural vulnerability, is the diagnosis of the causes of crack patterns. This is also due to the excessive complexity of models based on classical structural mechanics that makes them inappropriate especially when there is the necessity to perform a rapid vulnerability assessment at the territorial scale. This is why, a new approach, based on a ‘simple model’ (i.e. the Load Path Method, LPM), has been proposed by Palmisano and Elia for the interpretation of the behaviour of masonry buildings subjected to landslide-induced settlements. However, the LPM is very useful for rapidly finding the 'most plausible solution' instead of the exact solution. To find the solution, optimization algorithms are necessary. In this scenario, this article aims to show how the Bidirectional Evolutionary Structural Optimization method by Huang and Xie, can be very useful to optimize the strut-and-tie models obtained by using the Load Path Method.

Potential energy function for CH3+CH3 ⇆ C2H6: Attributes of the minimum energy path

NASA Astrophysics Data System (ADS)

Robertson, S. H.; Wardlaw, D. M.; Hirst, D. M.

1993-11-01

The region of the potential energy surface for the title reaction in the vicinity of its minimum energy path has been predicted from the analysis of ab initio electronic energy calculations. The ab initio procedure employs a 6-31G** basis set and a configuration interaction calculation which uses the orbitals obtained in a generalized valence bond calculation. Calculated equilibrium properties of ethane and of isolated methyl radical are compared to existing theoretical and experimental results. The reaction coordinate is represented by the carbon-carbon interatomic distance. The following attributes are reported as a function of this distance and fit to functional forms which smoothly interpolate between reactant and product values of each attribute: the minimum energy path potential, the minimum energy path geometry, normal mode frequencies for vibrational motion orthogonal to the reaction coordinate, a torsional potential, and a fundamental anharmonic frequency for local mode, out-of-plane CH3 bending (umbrella motion). The best representation is provided by a three-parameter modified Morse function for the minimum energy path potential and a two-parameter hyperbolic tangent switching function for all other attributes. A poorer but simpler representation, which may be satisfactory for selected applications, is provided by a standard Morse function and a one-parameter exponential switching function. Previous applications of the exponential switching function to estimate the reaction coordinate dependence of the frequencies and geometry of this system have assumed the same value of the range parameter α for each property and have taken α to be less than or equal to the ``standard'' value of 1.0 Å-1. Based on the present analysis this is incorrect: The α values depend on the property and range from ˜1.2 to ˜1.8 Å-1.

Path finding methods accounting for stoichiometry in metabolic networks

PubMed Central

2011-01-01

Graph-based methods have been widely used for the analysis of biological networks. Their application to metabolic networks has been much discussed, in particular noting that an important weakness in such methods is that reaction stoichiometry is neglected. In this study, we show that reaction stoichiometry can be incorporated into path-finding approaches via mixed-integer linear programming. This major advance at the modeling level results in improved prediction of topological and functional properties in metabolic networks. PMID:21619601

Optimal Electrical Energy Slewing for Reaction Wheel Spacecraft

NASA Astrophysics Data System (ADS)

Marsh, Harleigh Christian

The results contained in this dissertation contribute to a deeper level of understanding to the energy required to slew a spacecraft using reaction wheels. This work addresses the fundamental manner in which spacecrafts are slewed (eigenaxis maneuvering), and demonstrates that this conventional maneuver can be dramatically improved upon in regards to reduction of energy, dissipative losses, as well as peak power. Energy is a fundamental resource that effects every asset, system, and subsystem upon a spacecraft, from the attitude control system which orients the spacecraft, to the communication subsystem to link with ground stations, to the payloads which collect scientific data. For a reaction wheel spacecraft, the attitude control system is a particularly heavy load on the power and energy resources on a spacecraft. The central focus of this dissertation is reducing the burden which the attitude control system places upon the spacecraft in regards to electrical energy, which is shown in this dissertation to be a challenging problem to computationally solve and analyze. Reducing power and energy demands can have a multitude of benefits, spanning from the initial design phase, to in-flight operations, to potentially extending the mission life of the spacecraft. This goal is approached from a practical standpoint apropos to an industry-flight setting. Metrics to measure electrical energy and power are developed which are in-line with the cost associated to operating reaction wheel based attitude control systems. These metrics are incorporated into multiple families of practical high-dimensional constrained nonlinear optimal control problems to reduce the electrical energy, as well as the instantaneous power burdens imposed by the attitude control system upon the spacecraft. Minimizing electrical energy is shown to be a problem in L1 optimal control which is nonsmooth in regards to state variables as well as the control. To overcome the challenge of nonsmoothness, a method is adopted in this dissertation to transform the nonsmooth minimum electrical energy problem into an equivalent smooth formulation, which then allows standard techniques in optimal control to solve and analyze the problem. Through numerically solving families of optimal control problems, the relationship between electrical energy and transfer time is identified and explored for both off-and on-eigenaxis maneuvering, under minimum dissipative losses as well as under minimum electrical energy. A trade space between on-and off-eigenaxis maneuvering is identified, from which is shown that agile near time optimal maneuvers exist within the energy budget associated with conventional eigenaxis maneuvering. Moreover, even for conventional eigenaxis maneuvering, energy requirements can be dramatically reduced by maneuvering off-eigenaxis. These results address one of the fundamental assumptions in the field of optimal path design verses conventional maneuver design. Two practical flight situations are addressed in this dissertation in regards to reducing energy and power: The case when the attitude of the spacecraft is predetermined, and the case where reaction wheels can not be directly controlled. For the setting where the attitude of spacecraft is on a predefined trajectory, it is demonstrated that reduced energy maneuvers are only attainable though the application of null-motions, which requires control of the reaction wheels. A computationally light formulation is developed minimizing the dissipative losses through the application of null motions. In the situation where the reaction wheels can not be directly controlled, it is demonstrated that energy consumption, dissipative losses, and peak-power loads, of the reaction-wheel array can each be reduced substantially by controlling the input to the attitude control system through attitude steering. It is demonstrated that the open loop trajectories correctly predict the closed loop response when tracked by an attitude control system which does not allow direct command of the reaction wheels.

Optimization of MLS receivers for multipath environments

NASA Technical Reports Server (NTRS)

Mcalpine, G. A.; Irwin, S. H.; NELSON; Roleyni, G.

1977-01-01

Optimal design studies of MLS angle-receivers and a theoretical design-study of MLS DME-receivers are reported. The angle-receiver results include an integration of the scan data processor and tracking filter components of the optimal receiver into a unified structure. An extensive simulation study comparing the performance of the optimal and threshold receivers in a wide variety of representative dynamical interference environments was made. The optimal receiver was generally superior. A simulation of the performance of the threshold and delay-and-compare receivers in various signal environments was performed. An analysis of combined errors due to lateral reflections from vertical structures with small differential path delays, specular ground reflections with neglible differential path delays, and thermal noise in the receivers is provided.

Optimal trajectory planning of free-floating space manipulator using differential evolution algorithm

NASA Astrophysics Data System (ADS)

Wang, Mingming; Luo, Jianjun; Fang, Jing; Yuan, Jianping

2018-03-01

The existence of the path dependent dynamic singularities limits the volume of available workspace of free-floating space robot and induces enormous joint velocities when such singularities are met. In order to overcome this demerit, this paper presents an optimal joint trajectory planning method using forward kinematics equations of free-floating space robot, while joint motion laws are delineated with application of the concept of reaction null-space. Bézier curve, in conjunction with the null-space column vectors, are applied to describe the joint trajectories. Considering the forward kinematics equations of the free-floating space robot, the trajectory planning issue is consequently transferred to an optimization issue while the control points to construct the Bézier curve are the design variables. A constrained differential evolution (DE) scheme with premature handling strategy is implemented to find the optimal solution of the design variables while specific objectives and imposed constraints are satisfied. Differ from traditional methods, we synthesize null-space and specialized curve to provide a novel viewpoint for trajectory planning of free-floating space robot. Simulation results are presented for trajectory planning of 7 degree-of-freedom (DOF) kinematically redundant manipulator mounted on a free-floating spacecraft and demonstrate the feasibility and effectiveness of the proposed method.

Thermal Stability of Al2O3/Silicone Composites as High-Temperature Encapsulants

NASA Astrophysics Data System (ADS)

Yao, Yiying

Underwater gliders are robust and long endurance ocean sampling platforms that are increasingly being deployed in coastal regions. This new environment is characterized by shallow waters and significant currents that can challenge the mobility of these efficient (but traditionally slow moving) vehicles. This dissertation aims to improve the performance of shallow water underwater gliders through path planning. The path planning problem is formulated for a dynamic particle (or "kinematic car") model. The objective is to identify the path which satisfies specified boundary conditions and minimizes a particular cost. Several cost functions are considered. The problem is addressed using optimal control theory. The length scales of interest for path planning are within a few turn radii. First, an approach is developed for planning minimum-time paths, for a fixed speed glider, that are sub-optimal but are guaranteed to be feasible in the presence of unknown time-varying currents. Next the minimum-time problem for a glider with speed controls, that may vary between the stall speed and the maximum speed, is solved. Last, optimal paths that minimize change in depth (equivalently, maximize range) are investigated. Recognizing that path planning alone cannot overcome all of the challenges associated with significant currents and shallow waters, the design of a novel underwater glider with improved capabilities is explored. A glider with a pneumatic buoyancy engine (allowing large, rapid buoyancy changes) and a cylindrical moving mass mechanism (generating large pitch and roll moments) is designed, manufactured, and tested to demonstrate potential improvements in speed and maneuverability.

Impulsive noise suppression in color images based on the geodesic digital paths

NASA Astrophysics Data System (ADS)

Smolka, Bogdan; Cyganek, Boguslaw

2015-02-01

In the paper a novel filtering design based on the concept of exploration of the pixel neighborhood by digital paths is presented. The paths start from the boundary of a filtering window and reach its center. The cost of transitions between adjacent pixels is defined in the hybrid spatial-color space. Then, an optimal path of minimum total cost, leading from pixels of the window's boundary to its center is determined. The cost of an optimal path serves as a degree of similarity of the central pixel to the samples from the local processing window. If a pixel is an outlier, then all the paths starting from the window's boundary will have high costs and the minimum one will also be high. The filter output is calculated as a weighted mean of the central pixel and an estimate constructed using the information on the minimum cost assigned to each image pixel. So, first the costs of optimal paths are used to build a smoothed image and in the second step the minimum cost of the central pixel is utilized for construction of the weights of a soft-switching scheme. The experiments performed on a set of standard color images, revealed that the efficiency of the proposed algorithm is superior to the state-of-the-art filtering techniques in terms of the objective restoration quality measures, especially for high noise contamination ratios. The proposed filter, due to its low computational complexity, can be applied for real time image denoising and also for the enhancement of video streams.

Theoretical Study of Tautomerization Reactions for the Ground and First Excited Electronic States of Adenine

NASA Technical Reports Server (NTRS)

Salter, Latasha M.; Chaban, Galina M.; Kwak, Dochan (Technical Monitor)

2002-01-01

Geometrical structures and energetic properties for different tautomers of adenine are calculated in this study, using multi-configurational wave functions. Both the ground and the lowest singlet excited state potential energy surfaces are studied. Four tautomeric forms are considered, and their energetic order is found to be different on the ground and the excited state potential energy surfaces. Minimum energy reaction paths are obtained for hydrogen atom transfer (tautomerization) reactions in the ground and the lowest excited electronic states. It is found that the barrier heights and the shapes of the reaction paths are different for the ground and the excited electronic states, suggesting that the probability of such tautomerization reaction is higher on the excited state potential energy surface. This tautomerization process should become possible in the presence of water or other polar solvent molecules and should play an important role in the photochemistry of adenine.

Fluid-loop reaction system

NASA Technical Reports Server (NTRS)

Lurie, Boris J. (Inventor); Schier, J. Alan (Inventor); Iskenderian, Theodore C. (Inventor)

1991-01-01

An improved fluid actuating system for imparting motion to a body such as a spacecraft is disclosed. The fluid actuating system consists of a fluid mass that may be controllably accelerated through at least one fluid path whereby an opposite acceleration is experienced by the spacecraft. For full control of the spacecraft's orientation, the system would include a plurality of fluid paths. The fluid paths may be circular or irregular, and the fluid paths may be located on the interior or exterior of the spacecraft.

NetPath: a public resource of curated signal transduction pathways

PubMed Central

2010-01-01

We have developed NetPath as a resource of curated human signaling pathways. As an initial step, NetPath provides detailed maps of a number of immune signaling pathways, which include approximately 1,600 reactions annotated from the literature and more than 2,800 instances of transcriptionally regulated genes - all linked to over 5,500 published articles. We anticipate NetPath to become a consolidated resource for human signaling pathways that should enable systems biology approaches. PMID:20067622

Effect of reflected and refracted signals on coherent underwater acoustic communication: results from the Kauai experiment (KauaiEx 2003).

PubMed

Rouseff, Daniel; Badiey, Mohsen; Song, Aijun

2009-11-01

The performance of a communications equalizer is quantified in terms of the number of acoustic paths that are treated as usable signal. The analysis uses acoustical and oceanographic data collected off the Hawaiian Island of Kauai. Communication signals were measured on an eight-element vertical array at two different ranges, 1 and 2 km, and processed using an equalizer based on passive time-reversal signal processing. By estimating the Rayleigh parameter, it is shown that all paths reflected by the sea surface at both ranges undergo incoherent scattering. It is demonstrated that some of these incoherently scattered paths are still useful for coherent communications. At range of 1 km, optimal communications performance is achieved when six acoustic paths are retained and all paths with more than one reflection off the sea surface are rejected. Consistent with a model that ignores loss from near-surface bubbles, the performance improves by approximately 1.8 dB when increasing the number of retained paths from four to six. The four-path results though are more stable and require less frequent channel estimation. At range of 2 km, ray refraction is observed and communications performance is optimal when some paths with two sea-surface reflections are retained.

Optimal Predictive Control for Path Following of a Full Drive-by-Wire Vehicle at Varying Speeds

NASA Astrophysics Data System (ADS)

SONG, Pan; GAO, Bolin; XIE, Shugang; FANG, Rui

2017-05-01

The current research of the global chassis control problem for the full drive-by-wire vehicle focuses on the control allocation (CA) of the four-wheel-distributed traction/braking/steering systems. However, the path following performance and the handling stability of the vehicle can be enhanced a step further by automatically adjusting the vehicle speed to the optimal value. The optimal solution for the combined longitudinal and lateral motion control (MC) problem is given. First, a new variable step-size spatial transformation method is proposed and utilized in the prediction model to derive the dynamics of the vehicle with respect to the road, such that the tracking errors can be explicitly obtained over the prediction horizon at varying speeds. Second, a nonlinear model predictive control (NMPC) algorithm is introduced to handle the nonlinear coupling between any two directions of the vehicular planar motion and computes the sequence of the optimal motion states for following the desired path. Third, a hierarchical control structure is proposed to separate the motion controller into a NMPC based path planner and a terminal sliding mode control (TSMC) based path follower. As revealed through off-line simulations, the hierarchical methodology brings nearly 1700% improvement in computational efficiency without loss of control performance. Finally, the control algorithm is verified through a hardware in-the-loop simulation system. Double-lane-change (DLC) test results show that by using the optimal predictive controller, the root-mean-square (RMS) values of the lateral deviations and the orientation errors can be reduced by 41% and 30%, respectively, comparing to those by the optimal preview acceleration (OPA) driver model with the non-preview speed-tracking method. Additionally, the average vehicle speed is increased by 0.26 km/h with the peak sideslip angle suppressed to 1.9°. This research proposes a novel motion controller, which provides the full drive-by-wire vehicle with better lane-keeping and collision-avoidance capabilities during autonomous driving.

Simulation based optimization on automated fibre placement process

NASA Astrophysics Data System (ADS)

Lei, Shi

2018-02-01

In this paper, a software simulation (Autodesk TruPlan & TruFiber) based method is proposed to optimize the automate fibre placement (AFP) process. Different types of manufacturability analysis are introduced to predict potential defects. Advanced fibre path generation algorithms are compared with respect to geometrically different parts. Major manufacturing data have been taken into consideration prior to the tool paths generation to achieve high success rate of manufacturing.

Is addiction a failure of rationality?

PubMed

Ferguson, Brian

2012-01-01

This note argues that addiction itself can be seen as a form of double failure, specifically the failure to stick to a predetermined optimal lifetime consumption path for an addictive commodity, which failure might be the result of bad luck, and the failure to adjust the level of consumption of the addictive commodity once the consumer is off their optimal path, which might be seen as a failure of judgment.

Springback effects during single point incremental forming: Optimization of the tool path

NASA Astrophysics Data System (ADS)

Giraud-Moreau, Laurence; Belchior, Jérémy; Lafon, Pascal; Lotoing, Lionel; Cherouat, Abel; Courtielle, Eric; Guines, Dominique; Maurine, Patrick

2018-05-01

Incremental sheet forming is an emerging process to manufacture sheet metal parts. This process is more flexible than conventional one and well suited for small batch production or prototyping. During the process, the sheet metal blank is clamped by a blank-holder and a small-size smooth-end hemispherical tool moves along a user-specified path to deform the sheet incrementally. Classical three-axis CNC milling machines, dedicated structure or serial robots can be used to perform the forming operation. Whatever the considered machine, large deviations between the theoretical shape and the real shape can be observed after the part unclamping. These deviations are due to both the lack of stiffness of the machine and residual stresses in the part at the end of the forming stage. In this paper, an optimization strategy of the tool path is proposed in order to minimize the elastic springback induced by residual stresses after unclamping. A finite element model of the SPIF process allowing the shape prediction of the formed part with a good accuracy is defined. This model, based on appropriated assumptions, leads to calculation times which remain compatible with an optimization procedure. The proposed optimization method is based on an iterative correction of the tool path. The efficiency of the method is shown by an improvement of the final shape.

An algorithm to locate optimal bond breaking points on a potential energy surface for applications in mechanochemistry and catalysis.

PubMed

Bofill, Josep Maria; Ribas-Ariño, Jordi; García, Sergio Pablo; Quapp, Wolfgang

2017-10-21

The reaction path of a mechanically induced chemical transformation changes under stress. It is well established that the force-induced structural changes of minima and saddle points, i.e., the movement of the stationary points on the original or stress-free potential energy surface, can be described by a Newton Trajectory (NT). Given a reactive molecular system, a well-fitted pulling direction, and a sufficiently large value of the force, the minimum configuration of the reactant and the saddle point configuration of a transition state collapse at a point on the corresponding NT trajectory. This point is called barrier breakdown point or bond breaking point (BBP). The Hessian matrix at the BBP has a zero eigenvector which coincides with the gradient. It indicates which force (both in magnitude and direction) should be applied to the system to induce the reaction in a barrierless process. Within the manifold of BBPs, there exist optimal BBPs which indicate what is the optimal pulling direction and what is the minimal magnitude of the force to be applied for a given mechanochemical transformation. Since these special points are very important in the context of mechanochemistry and catalysis, it is crucial to develop efficient algorithms for their location. Here, we propose a Gauss-Newton algorithm that is based on the minimization of a positively defined function (the so-called σ-function). The behavior and efficiency of the new algorithm are shown for 2D test functions and for a real chemical example.

Quadcopter Path Following Control Design Using Output Feedback with Command Generator Tracker LOS Based At Square Path

NASA Astrophysics Data System (ADS)

Nugraha, A. T.; Agustinah, T.

2018-01-01

Quadcopter an unstable system, underactuated and nonlinear in quadcopter control research developments become an important focus of attention. In this study, following the path control method for position on the X and Y axis, used structure-Generator Tracker Command (CGT) is tested. Attitude control and position feedback quadcopter is compared using the optimal output. The addition of the H∞ performance optimal output feedback control is used to maintain the stability and robustness of quadcopter. Iterative numerical techniques Linear Matrix Inequality (LMI) is used to find the gain controller. The following path control problems is solved using the method of LQ regulators with output feedback. Simulations show that the control system can follow the paths that have been defined in the form of a reference signal square shape. The result of the simulation suggest that the method which used can bring the yaw angle at the expected value algorithm. Quadcopter can do automatically following path with cross track error mean X=0.5 m and Y=0.2 m.

Nanoscale imaging of clinical specimens using pathology-optimized expansion microscopy

PubMed Central

Zhao, Yongxin; Bucur, Octavian; Irshad, Humayun; Chen, Fei; Weins, Astrid; Stancu, Andreea L.; Oh, Eun-Young; DiStasio, Marcello; Torous, Vanda; Glass, Benjamin; Stillman, Isaac E.; Schnitt, Stuart J.; Beck, Andrew H.; Boyden, Edward S.

2017-01-01

Expansion microscopy (ExM), a method for improving the resolution of light microscopy by physically expanding the specimen, has not been applied to clinical tissue samples. Here we report a clinically optimized form of ExM that supports nanoscale imaging of human tissue specimens that have been fixed with formalin, embedded in paraffin, stained with hematoxylin and eosin (H&E), and/or fresh frozen. The method, which we call expansion pathology (ExPath), converts clinical samples into an ExM-compatible state, then applies an ExM protocol with protein anchoring and mechanical homogenization steps optimized for clinical samples. ExPath enables ~70 nm resolution imaging of diverse biomolecules in intact tissues using conventional diffraction-limited microscopes, and standard antibody and fluorescent DNA in situ hybridization reagents. We use ExPath for optical diagnosis of kidney minimal-change disease, which previously required electron microscopy (EM), and demonstrate high-fidelity computational discrimination between early breast neoplastic lesions that to date have challenged human judgment. ExPath may enable the routine use of nanoscale imaging in pathology and clinical research. PMID:28714966

A star recognition method based on the Adaptive Ant Colony algorithm for star sensors.

PubMed

Quan, Wei; Fang, Jiancheng

2010-01-01

A new star recognition method based on the Adaptive Ant Colony (AAC) algorithm has been developed to increase the star recognition speed and success rate for star sensors. This method draws circles, with the center of each one being a bright star point and the radius being a special angular distance, and uses the parallel processing ability of the AAC algorithm to calculate the angular distance of any pair of star points in the circle. The angular distance of two star points in the circle is solved as the path of the AAC algorithm, and the path optimization feature of the AAC is employed to search for the optimal (shortest) path in the circle. This optimal path is used to recognize the stellar map and enhance the recognition success rate and speed. The experimental results show that when the position error is about 50″, the identification success rate of this method is 98% while the Delaunay identification method is only 94%. The identification time of this method is up to 50 ms.

Nanoscale imaging of clinical specimens using pathology-optimized expansion microscopy.

PubMed

Zhao, Yongxin; Bucur, Octavian; Irshad, Humayun; Chen, Fei; Weins, Astrid; Stancu, Andreea L; Oh, Eun-Young; DiStasio, Marcello; Torous, Vanda; Glass, Benjamin; Stillman, Isaac E; Schnitt, Stuart J; Beck, Andrew H; Boyden, Edward S

2017-08-01

Expansion microscopy (ExM), a method for improving the resolution of light microscopy by physically expanding a specimen, has not been applied to clinical tissue samples. Here we report a clinically optimized form of ExM that supports nanoscale imaging of human tissue specimens that have been fixed with formalin, embedded in paraffin, stained with hematoxylin and eosin, and/or fresh frozen. The method, which we call expansion pathology (ExPath), converts clinical samples into an ExM-compatible state, then applies an ExM protocol with protein anchoring and mechanical homogenization steps optimized for clinical samples. ExPath enables ∼70-nm-resolution imaging of diverse biomolecules in intact tissues using conventional diffraction-limited microscopes and standard antibody and fluorescent DNA in situ hybridization reagents. We use ExPath for optical diagnosis of kidney minimal-change disease, a process that previously required electron microscopy, and we demonstrate high-fidelity computational discrimination between early breast neoplastic lesions for which pathologists often disagree in classification. ExPath may enable the routine use of nanoscale imaging in pathology and clinical research.

Efficient evaluation of atom tunneling combined with electronic structure calculations.

PubMed

Ásgeirsson, Vilhjálmur; Arnaldsson, Andri; Jónsson, Hannes

2018-03-14

Methodology for finding optimal tunneling paths and evaluating tunneling rates for atomic rearrangements is described. First, an optimal JWKB tunneling path for a system with fixed energy is obtained using a line integral extension of the nudged elastic band method. Then, a calculation of the dynamics along the path is used to determine the temperature at which it corresponds to an optimal Feynman path for thermally activated tunneling (instanton) and a harmonic approximation is used to estimate the transition rate. The method is illustrated with calculations for a modified two-dimensional Müller-Brown surface but is efficient enough to be used in combination with electronic structure calculations of the energy and atomic forces in systems containing many atoms. An example is presented where tunneling is the dominant mechanism well above room temperature as an H 3 BNH 3 molecule dissociates to form H 2 . Also, a solid-state example is presented where density functional theory calculations of H atom tunneling in a Ta crystal give close agreement with experimental measurements on hydrogen diffusion over a wide range in temperature.

Parameters governing ruthenium sawhorse-based decarboxylation of oleic acid

USDA-ARS?s Scientific Manuscript database

Ruthenium-catalyzed decarboxylation of 9-cisoctadecenoic is a path to produce biobased olefins. Here, a mechanistic study of this reaction was undertaken utilizing a closed reaction system and a pressure reactor. The proposed mechanism of an isomerization followed by a decarboxylation reaction was c...

Traffic-engineering-aware shortest-path routing and its application in IP-over-WDM networks [Invited

NASA Astrophysics Data System (ADS)

Lee, Youngseok; Mukherjee, Biswanath

2004-03-01

Single shortest-path routing is known to perform poorly for Internet traffic engineering (TE) where the typical optimization objective is to minimize the maximum link load. Splitting traffic uniformly over equal-cost multiple shortest paths in open shortest path first and intermediate system-intermediate system protocols does not always minimize the maximum link load when multiple paths are not carefully selected for the global traffic demand matrix. However, a TE-aware shortest path among all the equal-cost multiple shortest paths between each ingress-egress pair can be selected such that the maximum link load is significantly reduced. IP routers can use the globally optimal TE-aware shortest path without any change to existing routing protocols and without any serious configuration overhead. While calculating TE-aware shortest paths, the destination-based forwarding constraint at a node should be satisfied, because an IP router will forward a packet to the next hop toward the destination by looking up the destination prefix. We present a mathematical problem formulation for finding a set of TE-aware shortest paths for the given network as an integer linear program, and we propose a simple heuristic for solving large instances of the problem. Then we explore the usage of our proposed algorithm for the integrated TE method in IP-over-WDM networks. The proposed algorithm is evaluated through simulations in IP networks as well as in IP-over-WDM networks.

Path Planning Algorithms for Autonomous Border Patrol Vehicles

NASA Astrophysics Data System (ADS)

Lau, George Tin Lam

This thesis presents an online path planning algorithm developed for unmanned vehicles in charge of autonomous border patrol. In this Pursuit-Evasion game, the unmanned vehicle is required to capture multiple trespassers on its own before any of them reach a target safe house where they are safe from capture. The problem formulation is based on Isaacs' Target Guarding problem, but extended to the case of multiple evaders. The proposed path planning method is based on Rapidly-exploring random trees (RRT) and is capable of producing trajectories within several seconds to capture 2 or 3 evaders. Simulations are carried out to demonstrate that the resulting trajectories approach the optimal solution produced by a nonlinear programming-based numerical optimal control solver. Experiments are also conducted on unmanned ground vehicles to show the feasibility of implementing the proposed online path planning algorithm on physical applications.

Tracking trade transactions in water resource systems: A node-arc optimization formulation

NASA Astrophysics Data System (ADS)

Erfani, Tohid; Huskova, Ivana; Harou, Julien J.

2013-05-01

We formulate and apply a multicommodity network flow node-arc optimization model capable of tracking trade transactions in complex water resource systems. The model uses a simple node to node network connectivity matrix and does not require preprocessing of all possible flow paths in the network. We compare the proposed node-arc formulation with an existing arc-path (flow path) formulation and explain the advantages and difficulties of both approaches. We verify the proposed formulation model on a hypothetical water distribution network. Results indicate the arc-path model solves the problem with fewer constraints, but the proposed formulation allows using a simple network connectivity matrix which simplifies modeling large or complex networks. The proposed algorithm allows converting existing node-arc hydroeconomic models that broadly represent water trading to ones that also track individual supplier-receiver relationships (trade transactions).

Development of a new integrated local trajectory planning and tracking control framework for autonomous ground vehicles

NASA Astrophysics Data System (ADS)

Li, Xiaohui; Sun, Zhenping; Cao, Dongpu; Liu, Daxue; He, Hangen

2017-03-01

This study proposes a novel integrated local trajectory planning and tracking control (ILTPTC) framework for autonomous vehicles driving along a reference path with obstacles avoidance. For this ILTPTC framework, an efficient state-space sampling-based trajectory planning scheme is employed to smoothly follow the reference path. A model-based predictive path generation algorithm is applied to produce a set of smooth and kinematically-feasible paths connecting the initial state with the sampling terminal states. A velocity control law is then designed to assign a speed value at each of the points along the generated paths. An objective function considering both safety and comfort performance is carefully formulated for assessing the generated trajectories and selecting the optimal one. For accurately tracking the optimal trajectory while overcoming external disturbances and model uncertainties, a combined feedforward and feedback controller is developed. Both simulation analyses and vehicle testing are performed to verify the effectiveness of the proposed ILTPTC framework, and future research is also briefly discussed.

A theoretical study of three gas-phase reactions involving the production or loss of methane cations.

PubMed

Baptista, Leonardo; da Silveira, Enio F

2014-10-21

Hydrocarbon ions are important species in flames, spectroscopy and the interstellar medium. Their importance is reflected in the extensive body of literature on the structure and reactivity of carbocations. However, the geometry, electronic structure and reactivity of carbocations are difficult to assess. This study aims to contribute to the current knowledge of this subject by presenting a quantum mechanics description of methane cation dissociation using multiconfigurational methods. The geometric and electronic parameters of the minimum structure were determined for three main reaction paths: the dissociation CH4(+)→ CH2(+) + H2 and the dissociation-recombination processes CH4(+)↔ CH3(+) + H. The electronic and energetic effects of these reactions were analyzed, and it was found that each reaction path has a strong dependence on the methodology used as well as a strong multiconfigurational character during dissociation. The first doublet excited states are inner-shell excited states and may correspond to the ions that are expected to be formed after electron detachment. The rate coefficient for each reaction path was determined using variational transition state theory and RRKM/master equation calculations. The major dissociation paths, with their rate coefficients at the high-pressure limit, are CH4(+)(X(~)(2)B1) → CH3(+)(A(2)A1') + H((2)S) (k∞(T) = 1.42 × 10(+14) s(-1) exp(-37.12/RT)) and CH4(+)(X(~)(2)B1) → CH2(+)(A(2)A1) + H2((2)Σg(+)) (k∞(T) = 9.18 × 10(+14) s(-1) exp(-55.77/RT)). Our findings help to explain the abundance of ions formed from CH4 in the interstellar medium and to build models of chemical evolution.

Theoretical studies of mechanisms of cycloaddition reaction between difluoromethylene carbene and acetone

NASA Astrophysics Data System (ADS)

Lu, Xiu Hui; Yu, Hai Bin; Wu, Wei Rong; Xu, Yue Hua

Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second-order Møller-Plesset (MP2)/6-31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero-point energy (ZPE) and CCSD(T)/6-31G* single-point calculations. From the PES obtained with the CCSD(T)//MP2/6-31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four-membered ring intermediate, INT2, which is a barrier-free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four-membered product P2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier-free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier-free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P3 via a transition state TS3 with an energy barrier of 25.8 kJ/mol.

Optimal path planning for a mobile robot using cuckoo search algorithm

NASA Astrophysics Data System (ADS)

Mohanty, Prases K.; Parhi, Dayal R.

2016-03-01

The shortest/optimal path planning is essential for efficient operation of autonomous vehicles. In this article, a new nature-inspired meta-heuristic algorithm has been applied for mobile robot path planning in an unknown or partially known environment populated by a variety of static obstacles. This meta-heuristic algorithm is based on the levy flight behaviour and brood parasitic behaviour of cuckoos. A new objective function has been formulated between the robots and the target and obstacles, which satisfied the conditions of obstacle avoidance and target-seeking behaviour of robots present in the terrain. Depending upon the objective function value of each nest (cuckoo) in the swarm, the robot avoids obstacles and proceeds towards the target. The smooth optimal trajectory is framed with this algorithm when the robot reaches its goal. Some simulation and experimental results are presented at the end of the paper to show the effectiveness of the proposed navigational controller.

Minimal entropy probability paths between genome families.

PubMed

Ahlbrandt, Calvin; Benson, Gary; Casey, William

2004-05-01

We develop a metric for probability distributions with applications to biological sequence analysis. Our distance metric is obtained by minimizing a functional defined on the class of paths over probability measures on N categories. The underlying mathematical theory is connected to a constrained problem in the calculus of variations. The solution presented is a numerical solution, which approximates the true solution in a set of cases called rich paths where none of the components of the path is zero. The functional to be minimized is motivated by entropy considerations, reflecting the idea that nature might efficiently carry out mutations of genome sequences in such a way that the increase in entropy involved in transformation is as small as possible. We characterize sequences by frequency profiles or probability vectors, in the case of DNA where N is 4 and the components of the probability vector are the frequency of occurrence of each of the bases A, C, G and T. Given two probability vectors a and b, we define a distance function based as the infimum of path integrals of the entropy function H( p) over all admissible paths p(t), 0 < or = t< or =1, with p(t) a probability vector such that p(0)=a and p(1)=b. If the probability paths p(t) are parameterized as y(s) in terms of arc length s and the optimal path is smooth with arc length L, then smooth and "rich" optimal probability paths may be numerically estimated by a hybrid method of iterating Newton's method on solutions of a two point boundary value problem, with unknown distance L between the abscissas, for the Euler-Lagrange equations resulting from a multiplier rule for the constrained optimization problem together with linear regression to improve the arc length estimate L. Matlab code for these numerical methods is provided which works only for "rich" optimal probability vectors. These methods motivate a definition of an elementary distance function which is easier and faster to calculate, works on non-rich vectors, does not involve variational theory and does not involve differential equations, but is a better approximation of the minimal entropy path distance than the distance //b-a//(2). We compute minimal entropy distance matrices for examples of DNA myostatin genes and amino-acid sequences across several species. Output tree dendograms for our minimal entropy metric are compared with dendograms based on BLAST and BLAST identity scores.

The Optimal Capital Stock and Consumption Evolution for Non Zero Consumers Growth Rate in the Framework of Ramsey Model on Finite Horizon

NASA Astrophysics Data System (ADS)

Bonchiş, N.; Balint, Şt.

2010-09-01

In this paper the Ramsey optimal growth of the capital stock and consumption on finite horizon is analyzed when the growth rate of consumers is strictly positive. The main purpose is to establish the dependence of the optimal capital stock and consumption evolution on the growth rate of consumers. The analysis reveals: for any initial value k0≥0 there exists a unique optimal evolution path of length N+1 for the capital stock; if k0 is strictly positive then all the elements of the optimal capital stock evolution path are strictly positives except the last one which is zero; the optimal capital stock evolution of length N+1 starting from k0≥0 satisfies the Euler equation; the value function VN is strictly increasing, strictly concave and continuous on R+. The family of functions {VN-T}T = 0…N-1 satisfies the Bellman equation and it is the unique solution of this equation which is both continuous and satisfies the transversality condition. The Mangasarian Lemma is also satisfied. For N tending to infinity the optimal evolution path of length N of the capital stock tends to those on the infinite time horizon. For any k0>0 the value function in k0 decreases when the consumers growth rate increases.

A new optimization tool path planning for 3-axis end milling of free-form surfaces based on efficient machining intervals

NASA Astrophysics Data System (ADS)

Vu, Duy-Duc; Monies, Frédéric; Rubio, Walter

2018-05-01

A large number of studies, based on 3-axis end milling of free-form surfaces, seek to optimize tool path planning. Approaches try to optimize the machining time by reducing the total tool path length while respecting the criterion of the maximum scallop height. Theoretically, the tool path trajectories that remove the most material follow the directions in which the machined width is the largest. The free-form surface is often considered as a single machining area. Therefore, the optimization on the entire surface is limited. Indeed, it is difficult to define tool trajectories with optimal feed directions which generate largest machined widths. Another limiting point of previous approaches for effectively reduce machining time is the inadequate choice of the tool. Researchers use generally a spherical tool on the entire surface. However, the gains proposed by these different methods developed with these tools lead to relatively small time savings. Therefore, this study proposes a new method, using toroidal milling tools, for generating toolpaths in different regions on the machining surface. The surface is divided into several regions based on machining intervals. These intervals ensure that the effective radius of the tool, at each cutter-contact points on the surface, is always greater than the radius of the tool in an optimized feed direction. A parallel plane strategy is then used on the sub-surfaces with an optimal specific feed direction for each sub-surface. This method allows one to mill the entire surface with efficiency greater than with the use of a spherical tool. The proposed method is calculated and modeled using Maple software to find optimal regions and feed directions in each region. This new method is tested on a free-form surface. A comparison is made with a spherical cutter to show the significant gains obtained with a toroidal milling cutter. Comparisons with CAM software and experimental validations are also done. The results show the efficiency of the method.

From Bunsen Burners to Fuel Cells: Invoking Energy Transducers to Exemplify "Paths" and Unify the Energy-Related Concepts of Thermochemistry and Thermodynamics

ERIC Educational Resources Information Center

Hladky, Paul W.

2009-01-01

The conversion of chemical energy entirely into thermal energy by Bunsen burners and into thermal energy and electrical energy by fuel cells of varying efficiencies illustrates different paths by which a chemical reaction can occur. Using the efficiency of producing electrical energy as a path label allows all of the energy-related quantities to…

Toward Determining ATPase Mechanism in ABC Transporters: Development of the Reaction Path–Force Matching QM/MM Method

PubMed Central

Zhou, Y.; Ojeda-May, P.; Nagaraju, M.; Pu, J.

2016-01-01

Adenosine triphosphate (ATP)-binding cassette (ABC) transporters are ubiquitous ATP-dependent membrane proteins involved in translocations of a wide variety of substrates across cellular membranes. To understand the chemomechanical coupling mechanism as well as functional asymmetry in these systems, a quantitative description of how ABC transporters hydrolyze ATP is needed. Complementary to experimental approaches, computer simulations based on combined quantum mechanical and molecular mechanical (QM/MM) potentials have provided new insights into the catalytic mechanism in ABC transporters. Quantitatively reliable determination of the free energy requirement for enzymatic ATP hydrolysis, however, requires substantial statistical sampling on QM/MM potential. A case study shows that brute force sampling of ab initio QM/MM (AI/MM) potential energy surfaces is computationally impractical for enzyme simulations of ABC transporters. On the other hand, existing semiempirical QM/MM (SE/MM) methods, although affordable for free energy sampling, are unreliable for studying ATP hydrolysis. To close this gap, a multiscale QM/MM approach named reaction path–force matching (RP–FM) has been developed. In RP–FM, specific reaction parameters for a selected SE method are optimized against AI reference data along reaction paths by employing the force matching technique. The feasibility of the method is demonstrated for a proton transfer reaction in the gas phase and in solution. The RP–FM method may offer a general tool for simulating complex enzyme systems such as ABC transporters. PMID:27498639

New Polyazine-Bridged RuII,RhIII and RuII,RhI Supramolecular Photocatalysts for Water Reduction to Hydrogen Applicable for Solar Energy Conversion and Mechanistic Investigation of the Photocatalytic Cycle

NASA Astrophysics Data System (ADS)

Zhou, Rongwei

Underwater gliders are robust and long endurance ocean sampling platforms that are increasingly being deployed in coastal regions. This new environment is characterized by shallow waters and significant currents that can challenge the mobility of these efficient (but traditionally slow moving) vehicles. This dissertation aims to improve the performance of shallow water underwater gliders through path planning. The path planning problem is formulated for a dynamic particle (or "kinematic car") model. The objective is to identify the path which satisfies specified boundary conditions and minimizes a particular cost. Several cost functions are considered. The problem is addressed using optimal control theory. The length scales of interest for path planning are within a few turn radii. First, an approach is developed for planning minimum-time paths, for a fixed speed glider, that are sub-optimal but are guaranteed to be feasible in the presence of unknown time-varying currents. Next the minimum-time problem for a glider with speed controls, that may vary between the stall speed and the maximum speed, is solved. Last, optimal paths that minimize change in depth (equivalently, maximize range) are investigated. Recognizing that path planning alone cannot overcome all of the challenges associated with significant currents and shallow waters, the design of a novel underwater glider with improved capabilities is explored. A glider with a pneumatic buoyancy engine (allowing large, rapid buoyancy changes) and a cylindrical moving mass mechanism (generating large pitch and roll moments) is designed, manufactured, and tested to demonstrate potential improvements in speed and maneuverability.

Variational transition state theory: theoretical framework and recent developments.

PubMed

Bao, Junwei Lucas; Truhlar, Donald G

2017-12-11

This article reviews the fundamentals of variational transition state theory (VTST), its recent theoretical development, and some modern applications. The theoretical methods reviewed here include multidimensional quantum mechanical tunneling, multistructural VTST (MS-VTST), multi-path VTST (MP-VTST), both reaction-path VTST (RP-VTST) and variable reaction coordinate VTST (VRC-VTST), system-specific quantum Rice-Ramsperger-Kassel theory (SS-QRRK) for predicting pressure-dependent rate constants, and VTST in the solid phase, liquid phase, and enzymes. We also provide some perspectives regarding the general applicability of VTST.

The Path of Carbon in Photosynthesis IX. Photosynthesis, Photoreduction, and the Hydrogen-Oxygen-Carbon Dioxide Dark Reaction

DOE R&D Accomplishments Database

Badin, E. J.; Calvin, M.

1950-02-01

A comparison of the rates of fixation of Carbon 14 dioxide in algae for the processes of photosynthesis, photoreduction and the hydrogen-oxygen-carbon dioxide dark reaction has been made. For the same series of experiments, rates of incorporation of tracer carbon into the separate soluble components using the radiogram method have been determined. The mechanism of carbon dioxide uptake has been shown to occur via two distinct paths. In all cases studied, essentially the same compounds appear radioactive. The distribution with time, however, differs markedly.

Formation of furan fatty alkyl esters from their bis-epoxide fatty esters

USDA-ARS?s Scientific Manuscript database

Epoxidation of vegetable oils and consecutive epoxide ring-opening reaction is a widely investigated path for producing biobased lubricants and polymers. The reaction mechanism and products are considered well-studied and known. In the current study, the reactions of epoxidized alkyl soyate with fou...

Ancient village fire escape path planning based on improved ant colony algorithm

NASA Astrophysics Data System (ADS)

Xia, Wei; Cao, Kang; Hu, QianChuan

2017-06-01

The roadways are narrow and perplexing in ancient villages, it brings challenges and difficulties for people to choose route to escape when a fire occurs. In this paper, a fire escape path planning method based on ant colony algorithm is presented according to the problem. The factors in the fire environment which influence the escape speed is introduced to improve the heuristic function of the algorithm, optimal transfer strategy, and adjustment pheromone volatile factor to improve pheromone update strategy adaptively, improve its dynamic search ability and search speed. Through simulation, the dynamic adjustment of the optimal escape path is obtained, and the method is proved to be feasible.

Sequential Injection Analysis for Optimization of Molecular Biology Reactions

PubMed Central

Allen, Peter B.; Ellington, Andrew D.

2011-01-01

In order to automate the optimization of complex biochemical and molecular biology reactions, we developed a Sequential Injection Analysis (SIA) device and combined this with a Design of Experiment (DOE) algorithm. This combination of hardware and software automatically explores the parameter space of the reaction and provides continuous feedback for optimizing reaction conditions. As an example, we optimized the endonuclease digest of a fluorogenic substrate, and showed that the optimized reaction conditions also applied to the digest of the substrate outside of the device, and to the digest of a plasmid. The sequential technique quickly arrived at optimized reaction conditions with less reagent use than a batch process (such as a fluid handling robot exploring multiple reaction conditions in parallel) would have. The device and method should now be amenable to much more complex molecular biology reactions whose variable spaces are correspondingly larger. PMID:21338059

An adaptive multi-level simulation algorithm for stochastic biological systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lester, C., E-mail: lesterc@maths.ox.ac.uk; Giles, M. B.; Baker, R. E.

2015-01-14

Discrete-state, continuous-time Markov models are widely used in the modeling of biochemical reaction networks. Their complexity often precludes analytic solution, and we rely on stochastic simulation algorithms (SSA) to estimate system statistics. The Gillespie algorithm is exact, but computationally costly as it simulates every single reaction. As such, approximate stochastic simulation algorithms such as the tau-leap algorithm are often used. Potentially computationally more efficient, the system statistics generated suffer from significant bias unless tau is relatively small, in which case the computational time can be comparable to that of the Gillespie algorithm. The multi-level method [Anderson and Higham, “Multi-level Montemore » Carlo for continuous time Markov chains, with applications in biochemical kinetics,” SIAM Multiscale Model. Simul. 10(1), 146–179 (2012)] tackles this problem. A base estimator is computed using many (cheap) sample paths at low accuracy. The bias inherent in this estimator is then reduced using a number of corrections. Each correction term is estimated using a collection of paired sample paths where one path of each pair is generated at a higher accuracy compared to the other (and so more expensive). By sharing random variables between these paired paths, the variance of each correction estimator can be reduced. This renders the multi-level method very efficient as only a relatively small number of paired paths are required to calculate each correction term. In the original multi-level method, each sample path is simulated using the tau-leap algorithm with a fixed value of τ. This approach can result in poor performance when the reaction activity of a system changes substantially over the timescale of interest. By introducing a novel adaptive time-stepping approach where τ is chosen according to the stochastic behaviour of each sample path, we extend the applicability of the multi-level method to such cases. We demonstrate the efficiency of our method using a number of examples.« less

Liquid waveguide spectrophotometric measurement of nanomolar ammonium in seawater based on the indophenol reaction with o-phenylphenol (OPP).

PubMed

Hashihama, Fuminori; Kanda, Jota; Tauchi, Ami; Kodama, Taketoshi; Saito, Hiroaki; Furuya, Ken

2015-10-01

We describe a highly sensitive colorimetric method for the determination of nanomolar concentrations of ammonium in seawater based on the indophenol reaction with o-phenylphenol [(1,1'-biphenyl)-2-ol, abbreviated as OPP]. OPP is available as non-toxic, stable flaky crystals with no caustic odor and has some advantages over phenol in practical use. The method was established by using a gas-segmented continuous flow analyzer equipped with two types of long path liquid waveguide capillary cell, LWCCs (100 cm and 200 cm) and an UltraPath (200 cm), which have inner diameters of 0.55 mm and 2 mm, respectively. The reagent concentrations, flow rates of the pumping tubes, and reaction path and temperature were determined on the basis of a manual indophenol blue method with OPP (Kanda, Water Res. 29 (1995) 2746-2750). The sample mixed with reagents that form indophenol blue dye was measured at 670 nm. Aged subtropical surface water was used as a blank, a matrix of standards, and the carrier. The detection limits of the analytical systems with a 100 cm LWCC, a 200 cm LWCC, and a 200 cm UltraPath were 6, 4, and 4 nM, respectively. These systems had high precision (<4% at 100 nM) and a linear dynamic range up to 200 nM. Non-linear baseline drift did not occur when using the UltraPath system. This is due to the elimination of cell clogging because of the larger inner diameter of the UltraPath compared to the LWCCs. The UltraPath system is thus more suitable for long-term measurements compared with the LWCC systems. The results of the proposed sensitive colorimetry and a conventional colorimetry for the determination of seawater samples showed no significant difference. The proposed analytical systems were applied to underway surface monitoring and vertical observation in the oligotrophic South Pacific. Copyright © 2015 Elsevier B.V. All rights reserved.

Autonomous Control Modes and Optimized Path Guidance for Shipboard Landing in High Sea States

DTIC Science & Technology

2016-04-28

Contract # N00014-14-C-0004 Autonomous Control Modes and Optimized Path Guidance for Shipboard Landing in High Sea States Progress Report...Aviation (ONR BAA12-SN-0028). This project addresses the Sea Based Aviation (SBA) initiative in Advanced Handling Qualities for Rotorcraft. Landing a...and a degraded visual environment, workload during the landing task begins to approach the limits of a human pilot’s capability. It is a similarly

A statistical-based scheduling algorithm in automated data path synthesis

NASA Technical Reports Server (NTRS)

Jeon, Byung Wook; Lursinsap, Chidchanok

1992-01-01

In this paper, we propose a new heuristic scheduling algorithm based on the statistical analysis of the cumulative frequency distribution of operations among control steps. It has a tendency of escaping from local minima and therefore reaching a globally optimal solution. The presented algorithm considers the real world constraints such as chained operations, multicycle operations, and pipelined data paths. The result of the experiment shows that it gives optimal solutions, even though it is greedy in nature.

Light extraction efficiency of GaN-based LED with pyramid texture by using ray path analysis.

PubMed

Pan, Jui-Wen; Wang, Chia-Shen

2012-09-10

We study three different gallium-nitride (GaN) based light emitting diode (LED) cases based on the different locations of the pyramid textures. In case 1, the pyramid texture is located on the sapphire top surface, in case 2, the pyramid texture is locate on the P-GaN top surface, while in case 3, the pyramid texture is located on both the sapphire and P-GaN top surfaces. We study the relationship between the light extraction efficiency (LEE) and angle of slant of the pyramid texture. The optimization of total LEE was highest for case 3 among the three cases. Moreover, the seven escape paths along which most of the escaped photon flux propagated were selected in a simulation of the LEDs. The seven escape paths were used to estimate the slant angle for the optimization of LEE and to precisely analyze the photon escape path.

The path of placement of a removable partial denture: a microscope based approach to survey and design

PubMed Central

2015-01-01

This article reviews the topic of how to identify and develop a removable partial denture (RPD) path of placement, and provides a literature review of the concept of the RPD path of placement, also known as the path of insertion. An optimal RPD path of placement, guided by mutually parallel guide planes, ensures that the RPD flanges fit intimately over edentulous ridge structures and that the framework fits intimately with guide plane surfaces, which prevents food collecting empty spaces between the intaglio surface of the framework and intraoral surfaces, and ensures that RPD clasps engage adequate numbers of tooth undercuts to ensure RPD retention. The article covers topics such as the causes of obstructions to RPD intra-oral seating, the causes of food collecting empty spaces that may exist around an RPD, and how to identify if a guide plane is parallel with the projected RPD path of placement. The article presents a method of using a surgical operating microscope, or high magnification (6-8x or greater) binocular surgical loupes telescopes, combined with co-axial illumination, to identify a preliminary path of placement for an arch. This preliminary path of placement concept may help to guide a dentist or a dental laboratory technician when surveying a master cast of the arch to develop an RPD path of placement, or in verifying that intra-oral contouring has aligned teeth surfaces optimally with the RPD path of placement. In dentistry, a well-fitting RPD reduces long-term periodontal or structural damage to abutment teeth. PMID:25722842

Kudi: A free open-source python library for the analysis of properties along reaction paths.

PubMed

Vogt-Geisse, Stefan

2016-05-01

With increasing computational capabilities, an ever growing amount of data is generated in computational chemistry that contains a vast amount of chemically relevant information. It is therefore imperative to create new computational tools in order to process and extract this data in a sensible way. Kudi is an open source library that aids in the extraction of chemical properties from reaction paths. The straightforward structure of Kudi makes it easy to use for users and allows for effortless implementation of new capabilities, and extension to any quantum chemistry package. A use case for Kudi is shown for the tautomerization reaction of formic acid. Kudi is available free of charge at www.github.com/stvogt/kudi.

Curvature Continuous and Bounded Path Planning for Fixed-Wing UAVs

PubMed Central

Jiang, Peng; Li, Deshi; Sun, Tao

2017-01-01

Unmanned Aerial Vehicles (UAVs) play an important role in applications such as data collection and target reconnaissance. An accurate and optimal path can effectively increase the mission success rate in the case of small UAVs. Although path planning for UAVs is similar to that for traditional mobile robots, the special kinematic characteristics of UAVs (such as their minimum turning radius) have not been taken into account in previous studies. In this paper, we propose a locally-adjustable, continuous-curvature, bounded path-planning algorithm for fixed-wing UAVs. To deal with the curvature discontinuity problem, an optimal interpolation algorithm and a key-point shift algorithm are proposed based on the derivation of a curvature continuity condition. To meet the upper bound for curvature and to render the curvature extrema controllable, a local replanning scheme is designed by combining arcs and Bezier curves with monotonic curvature. In particular, a path transition mechanism is built for the replanning phase using minimum curvature circles for a planning philosophy. Numerical results demonstrate that the analytical planning algorithm can effectively generate continuous-curvature paths, while satisfying the curvature upper bound constraint and allowing UAVs to pass through all predefined waypoints in the desired mission region. PMID:28925960

Curvature Continuous and Bounded Path Planning for Fixed-Wing UAVs.

PubMed

Wang, Xiaoliang; Jiang, Peng; Li, Deshi; Sun, Tao

2017-09-19

Unmanned Aerial Vehicles (UAVs) play an important role in applications such as data collection and target reconnaissance. An accurate and optimal path can effectively increase the mission success rate in the case of small UAVs. Although path planning for UAVs is similar to that for traditional mobile robots, the special kinematic characteristics of UAVs (such as their minimum turning radius) have not been taken into account in previous studies. In this paper, we propose a locally-adjustable, continuous-curvature, bounded path-planning algorithm for fixed-wing UAVs. To deal with the curvature discontinuity problem, an optimal interpolation algorithm and a key-point shift algorithm are proposed based on the derivation of a curvature continuity condition. To meet the upper bound for curvature and to render the curvature extrema controllable, a local replanning scheme is designed by combining arcs and Bezier curves with monotonic curvature. In particular, a path transition mechanism is built for the replanning phase using minimum curvature circles for a planning philosophy. Numerical results demonstrate that the analytical planning algorithm can effectively generate continuous-curvature paths, while satisfying the curvature upper bound constraint and allowing UAVs to pass through all predefined waypoints in the desired mission region.

Dry (CO2) reforming of methane over Pt catalysts studied by DFT and kinetic modeling

NASA Astrophysics Data System (ADS)

Niu, Juntian; Du, Xuesen; Ran, Jingyu; Wang, Ruirui

2016-07-01

Dry reforming of methane (DRM) is a well-studied reaction that is of both scientific and industrial importance. In order to design catalysts that minimize the deactivation and improve the selectivity and activity for a high H2/CO yield, it is necessary to understand the elementary reaction steps involved in activation and conversion of CO2 and CH4. In our present work, a microkinetic model based on density functional theory (DFT) calculations is applied to explore the reaction mechanism for methane dry reforming on Pt catalysts. The adsorption energies of the reactants, intermediates and products, and the activation barriers for the elementary reactions involved in the DRM process are calculated over the Pt(1 1 1) surface. In the process of CH4 direct dissociation, the kinetic results show that CH dissociative adsorption on Pt(1 1 1) surface is the rate-determining step. CH appears to be the most abundant species on the Pt(1 1 1) surface, suggesting that carbon deposition is not easy to form in CH4 dehydrogenation on Pt(1 1 1) surface. In the process of CO2 activation, three possible reaction pathways are considered to contribute to the CO2 decomposition: (I) CO2* + * → CO* + O*; (II) CO2* + H* → COOH* + * → CO* + OH*; (III) CO2* + H* → mono-HCOO* + * → bi-HCOO* + * [CO2* + H* → bi-HCOO* + *] → CHO* + O*. Path I requires process to overcome the activation barrier of 1.809 eV and the forward reaction is calculated to be strongly endothermic by 1.430 eV. In addition, the kinetic results also indicate this process is not easy to proceed on Pt(1 1 1) surface. While the CO2 activation by H adsorbed over the catalyst surface to form COOH intermediate (Path II) is much easier to be carried out with the lower activation barrier of 0.746 eV. The Csbnd O bond scission is the rate-determining step along this pathway and the process needs to overcome the activation barrier of 1.522 eV. Path III reveals the CO2 activation through H adsorbed over the catalyst surface to form HCOO intermediate firstly. This reaction requires a quite high activation barrier and is a strongly endothermic process leading to a very low forward rate constant. In conclusion, Path II is the dominant reaction pathway in CO2 activation. Additionally, there are two pathways of CH oxidation by O: (A) CH* + O* → CHO* + * → CO* + H*; (B) CH* + O* → COH* + * → CO* + H*. Both the activation barriers and kinetic results demonstrate that Path A is the prior reaction pathway. Furthermore, in the two pathways of CH oxidation by OH: (C) CH* + OH* → CHOH* + * → CHO* + H*; (D) CH* + OH* → CHOH* + * → COH* + H*. Path C is easier to proceed. In conclusion, the main reaction pathway in CH oxidation according to the mechanism: CH* + OH* → CHOH* + * → CHO* + H* → CO* + 2H*. These results could provide some useful information for the operation of DRM over Pt catalysts, and are helpful to understand the mechanisms of DRM from the atomic scale.

The Edge-Disjoint Path Problem on Random Graphs by Message-Passing.

PubMed

Altarelli, Fabrizio; Braunstein, Alfredo; Dall'Asta, Luca; De Bacco, Caterina; Franz, Silvio

2015-01-01

We present a message-passing algorithm to solve a series of edge-disjoint path problems on graphs based on the zero-temperature cavity equations. Edge-disjoint paths problems are important in the general context of routing, that can be defined by incorporating under a unique framework both traffic optimization and total path length minimization. The computation of the cavity equations can be performed efficiently by exploiting a mapping of a generalized edge-disjoint path problem on a star graph onto a weighted maximum matching problem. We perform extensive numerical simulations on random graphs of various types to test the performance both in terms of path length minimization and maximization of the number of accommodated paths. In addition, we test the performance on benchmark instances on various graphs by comparison with state-of-the-art algorithms and results found in the literature. Our message-passing algorithm always outperforms the others in terms of the number of accommodated paths when considering non trivial instances (otherwise it gives the same trivial results). Remarkably, the largest improvement in performance with respect to the other methods employed is found in the case of benchmarks with meshes, where the validity hypothesis behind message-passing is expected to worsen. In these cases, even though the exact message-passing equations do not converge, by introducing a reinforcement parameter to force convergence towards a sub optimal solution, we were able to always outperform the other algorithms with a peak of 27% performance improvement in terms of accommodated paths. On random graphs, we numerically observe two separated regimes: one in which all paths can be accommodated and one in which this is not possible. We also investigate the behavior of both the number of paths to be accommodated and their minimum total length.

The Edge-Disjoint Path Problem on Random Graphs by Message-Passing

PubMed Central

2015-01-01

We present a message-passing algorithm to solve a series of edge-disjoint path problems on graphs based on the zero-temperature cavity equations. Edge-disjoint paths problems are important in the general context of routing, that can be defined by incorporating under a unique framework both traffic optimization and total path length minimization. The computation of the cavity equations can be performed efficiently by exploiting a mapping of a generalized edge-disjoint path problem on a star graph onto a weighted maximum matching problem. We perform extensive numerical simulations on random graphs of various types to test the performance both in terms of path length minimization and maximization of the number of accommodated paths. In addition, we test the performance on benchmark instances on various graphs by comparison with state-of-the-art algorithms and results found in the literature. Our message-passing algorithm always outperforms the others in terms of the number of accommodated paths when considering non trivial instances (otherwise it gives the same trivial results). Remarkably, the largest improvement in performance with respect to the other methods employed is found in the case of benchmarks with meshes, where the validity hypothesis behind message-passing is expected to worsen. In these cases, even though the exact message-passing equations do not converge, by introducing a reinforcement parameter to force convergence towards a sub optimal solution, we were able to always outperform the other algorithms with a peak of 27% performance improvement in terms of accommodated paths. On random graphs, we numerically observe two separated regimes: one in which all paths can be accommodated and one in which this is not possible. We also investigate the behavior of both the number of paths to be accommodated and their minimum total length. PMID:26710102

Robotic path-finding in inverse treatment planning for stereotactic radiosurgery with continuous dose delivery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vandewouw, Marlee M., E-mail: marleev@mie.utoronto

Purpose: Continuous dose delivery in radiation therapy treatments has been shown to decrease total treatment time while improving the dose conformity and distribution homogeneity over the conventional step-and-shoot approach. The authors develop an inverse treatment planning method for Gamma Knife® Perfexion™ that continuously delivers dose along a path in the target. Methods: The authors’ method is comprised of two steps: find a path within the target, then solve a mixed integer optimization model to find the optimal collimator configurations and durations along the selected path. Robotic path-finding techniques, specifically, simultaneous localization and mapping (SLAM) using an extended Kalman filter, aremore » used to obtain a path that travels sufficiently close to selected isocentre locations. SLAM is novelly extended to explore a 3D, discrete environment, which is the target discretized into voxels. Further novel extensions are incorporated into the steering mechanism to account for target geometry. Results: The SLAM method was tested on seven clinical cases and compared to clinical, Hamiltonian path continuous delivery, and inverse step-and-shoot treatment plans. The SLAM approach improved dose metrics compared to the clinical plans and Hamiltonian path continuous delivery plans. Beam-on times improved over clinical plans, and had mixed performance compared to Hamiltonian path continuous plans. The SLAM method is also shown to be robust to path selection inaccuracies, isocentre selection, and dose distribution. Conclusions: The SLAM method for continuous delivery provides decreased total treatment time and increased treatment quality compared to both clinical and inverse step-and-shoot plans, and outperforms existing path methods in treatment quality. It also accounts for uncertainty in treatment planning by accommodating inaccuracies.« less

Validation of RetroPath, a computer-aided design tool for metabolic pathway engineering.

PubMed

Fehér, Tamás; Planson, Anne-Gaëlle; Carbonell, Pablo; Fernández-Castané, Alfred; Grigoras, Ioana; Dariy, Ekaterina; Perret, Alain; Faulon, Jean-Loup

2014-11-01

Metabolic engineering has succeeded in biosynthesis of numerous commodity or high value compounds. However, the choice of pathways and enzymes used for production was many times made ad hoc, or required expert knowledge of the specific biochemical reactions. In order to rationalize the process of engineering producer strains, we developed the computer-aided design (CAD) tool RetroPath that explores and enumerates metabolic pathways connecting the endogenous metabolites of a chassis cell to the target compound. To experimentally validate our tool, we constructed 12 top-ranked enzyme combinations producing the flavonoid pinocembrin, four of which displayed significant yields. Namely, our tool queried the enzymes found in metabolic databases based on their annotated and predicted activities. Next, it ranked pathways based on the predicted efficiency of the available enzymes, the toxicity of the intermediate metabolites and the calculated maximum product flux. To implement the top-ranking pathway, our procedure narrowed down a list of nine million possible enzyme combinations to 12, a number easily assembled and tested. One round of metabolic network optimization based on RetroPath output further increased pinocembrin titers 17-fold. In total, 12 out of the 13 enzymes tested in this work displayed a relative performance that was in accordance with its predicted score. These results validate the ranking function of our CAD tool, and open the way to its utilization in the biosynthesis of novel compounds. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the ion-pair dissociation mechanisms in the small NaCl·(H2 O)6 cluster: A perspective from reaction path search calculations.

PubMed

Takayanagi, Toshiyuki; Nakatomi, Taiki; Yonetani, Yoshiteru

2018-04-20

We performed reaction path search calculations for the NaCl·(H 2 O) 6 cluster using the global reaction route mapping (GRRM) code to understand the atomic-level mechanisms of the NaCl → Na +  + Cl - ionic dissociation induced by water solvents. Low-lying minima, transition states connecting two local minima and corresponding intrinsic reaction coordinates on the potential energy surface are explored. We found that the NaCl distances at the transitions states for the dissociation pathways were distributed in a relatively wide range of 2.7-3.7 Å and that the NaCl distance at the transition state did not correlate with the commonly used solvation coordinates. This suggests that the definition of the transition states with specific structures as well as good reaction coordinate is very difficult for the ionic dissociation process even in a small water cluster. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

Branching and competition of ultrafast photochemical reactions of cyclooctatriene and bicyclooctadiene

NASA Astrophysics Data System (ADS)

Kosma, Kyriaki; Trushin, Sergei A.; Schmid, Wolfram E.; Fuß, Werner

2015-12-01

The main primary photoproducts of cycloocta-1,3,5-triene (COT) are a strained mono-E isomer, Z,Z-octatetraene (OT, from electrocyclic ring opening) and benzene + ethylene. We investigated the excited-state dynamics of COT by time-resolved mass spectroscopy, probing by near-IR photoionization. Unexpectedly, we found only one reaction channel. We assign it to the pericyclic reactions. Evidence for an early branching between this and the Z-E channel is taken from previous resonance Raman data. This channel confirms previously formulated rules on the excited states involved, the reaction path and driving forces and contributes to their rationalization. Bicyclo[4.2.0]octa-2,4-diene undergoes only two pericyclic reactions: ring opening to OT and cleavage to benzene + ethylene. We investigated it briefly in its equilibrium mixture with COT. The data are consistent with a common path on the excited surfaces. Suggestions are made for structures of conical intersections, and driving forces are considered. All processes were found to be barrierless.

Final Technical Report: Mathematical Foundations for Uncertainty Quantification in Materials Design

DOE Office of Scientific and Technical Information (OSTI.GOV)

Plechac, Petr; Vlachos, Dionisios G.

We developed path-wise information theory-based and goal-oriented sensitivity analysis and parameter identification methods for complex high-dimensional dynamics and in particular of non-equilibrium extended molecular systems. The combination of these novel methodologies provided the first methods in the literature which are capable to handle UQ questions for stochastic complex systems with some or all of the following features: (a) multi-scale stochastic models such as (bio)chemical reaction networks, with a very large number of parameters, (b) spatially distributed systems such as Kinetic Monte Carlo or Langevin Dynamics, (c) non-equilibrium processes typically associated with coupled physico-chemical mechanisms, driven boundary conditions, hybrid micro-macro systems,more » etc. A particular computational challenge arises in simulations of multi-scale reaction networks and molecular systems. Mathematical techniques were applied to in silico prediction of novel materials with emphasis on the effect of microstructure on model uncertainty quantification (UQ). We outline acceleration methods to make calculations of real chemistry feasible followed by two complementary tasks on structure optimization and microstructure-induced UQ.« less

Gender differences in loss of psychological resources following experimentally-induced vicarious stress.

PubMed

Ben-Zur, Hasida; Zeidner, Moshe

2012-07-01

The present research focuses on gender differences in resource loss, perceived threat, and negative affective reactions induced by experimental manipulation of vicarious stress. Israeli students (54.7% women) were randomly allocated to one of two conditions: (1) Threat Condition (n=98), in which participants were exposed to a video film depicting terror attacks and (2) Control Condition (n=30), in which participants viewed a video film depicting a series of non-emotive news broadcasts. Participants also completed measures of mastery, optimism, and self-esteem. The data indicated that whereas under the Threat Condition women scored lower on psychological resources and higher on perceived threat than men, no significant gender differences were observed under the Control Condition. A path analysis revealed that gender was directly related to perceived threat and resource loss, which, in turn, were related to negative affect. In addition, a greater sense of mastery was related to lower resource loss. Overall, these experimental findings suggest that gender and mastery bear prominent effects on cognitive and emotional reactions to vicarious life threat.

Dijkstra Methode for Optimalize Recommendation System of Garbage Transportation Time in Surakarta City

NASA Astrophysics Data System (ADS)

Hartatik; Purbayu, A.; Triyono, L.

2018-03-01

Major problem that often occurs in waste transportation in each region is the route of garbage transportation. Determination of this route should become a major concern because it affects fuel consumption and also the working time from the employee. Therefore, in this research we will develop an application to optimize with pigeonhole and dijsktra algorithm. Pigeonhole algorithm is used to determine which garbage trucks should be taken in a particular TPS. Time optimization is done by determining the shortest path that can be skipped for each garbage truck. Data generated from Pigeonhole then used to determine the shortest path by using Dijkstra algorithm.

MetaNET--a web-accessible interactive platform for biological metabolic network analysis.

PubMed

Narang, Pankaj; Khan, Shawez; Hemrom, Anmol Jaywant; Lynn, Andrew Michael

2014-01-01

Metabolic reactions have been extensively studied and compiled over the last century. These have provided a theoretical base to implement models, simulations of which are used to identify drug targets and optimize metabolic throughput at a systemic level. While tools for the perturbation of metabolic networks are available, their applications are limited and restricted as they require varied dependencies and often a commercial platform for full functionality. We have developed MetaNET, an open source user-friendly platform-independent and web-accessible resource consisting of several pre-defined workflows for metabolic network analysis. MetaNET is a web-accessible platform that incorporates a range of functions which can be combined to produce different simulations related to metabolic networks. These include (i) optimization of an objective function for wild type strain, gene/catalyst/reaction knock-out/knock-down analysis using flux balance analysis. (ii) flux variability analysis (iii) chemical species participation (iv) cycles and extreme paths identification and (v) choke point reaction analysis to facilitate identification of potential drug targets. The platform is built using custom scripts along with the open-source Galaxy workflow and Systems Biology Research Tool as components. Pre-defined workflows are available for common processes, and an exhaustive list of over 50 functions are provided for user defined workflows. MetaNET, available at http://metanet.osdd.net , provides a user-friendly rich interface allowing the analysis of genome-scale metabolic networks under various genetic and environmental conditions. The framework permits the storage of previous results, the ability to repeat analysis and share results with other users over the internet as well as run different tools simultaneously using pre-defined workflows, and user-created custom workflows.

Optimal multisensory decision-making in a reaction-time task.

PubMed

Drugowitsch, Jan; DeAngelis, Gregory C; Klier, Eliana M; Angelaki, Dora E; Pouget, Alexandre

2014-06-14

Humans and animals can integrate sensory evidence from various sources to make decisions in a statistically near-optimal manner, provided that the stimulus presentation time is fixed across trials. Little is known about whether optimality is preserved when subjects can choose when to make a decision (reaction-time task), nor when sensory inputs have time-varying reliability. Using a reaction-time version of a visual/vestibular heading discrimination task, we show that behavior is clearly sub-optimal when quantified with traditional optimality metrics that ignore reaction times. We created a computational model that accumulates evidence optimally across both cues and time, and trades off accuracy with decision speed. This model quantitatively explains subjects's choices and reaction times, supporting the hypothesis that subjects do, in fact, accumulate evidence optimally over time and across sensory modalities, even when the reaction time is under the subject's control.

Mechanistic Study of Nitric Oxide Reduction by Hydrogen on Pt(100) (I): A DFT Analysis of the Reaction Network

DOE PAGES

Bai, Yunhai; Mavrikakis, Manos

2017-05-08

Periodic, self-consistent density functional theory (DFT-GGA, PW91) calculations are used to study the reaction mechanism for nitric oxide (NO) reduction by hydrogen (H 2) on Pt(100). Energetics of various N–O activation paths, including both direct and hydrogen-assisted N–O bond-breaking paths, and the formation of three different N-containing products (N 2, N 2O, and NH3), are systematically studied. On the basis of our analysis, NO* dissociation has a lower barrier than NO* hydrogenation to HNO* or NOH*, and therefore, the direct NO dissociation path is predicted to dominate N–O activation on clean Pt(100). The reaction of atomic N* with N* andmore » NO* is proposed as the mechanism for N 2 and N 2O formation, respectively. NH 3 formation from N* via three successive hydrogenation steps is also studied and is found to be kinetically more difficult than N 2 and N 2O formation from N*. Finally, NO adsorption phase diagrams on Pt(100) are constructed, and these phase diagrams suggest that, at low temperatures (e.g., 400 K), the Pt(100) surface may be covered by half a monolayer of NO. We propose that high NO coverage might affect the NO + H 2 reaction mechanism, and therefore, one should explicitly take the NO coverage into consideration in first-principles studies to determine the reaction mechanism on catalyst surfaces under reaction conditions. In conclusion, a detailed analysis of high NO coverage effects on the reaction mechanism will be presented in a separate contribution.« less

Mechanistic Study of Nitric Oxide Reduction by Hydrogen on Pt(100) (I): A DFT Analysis of the Reaction Network

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bai, Yunhai; Mavrikakis, Manos

Periodic, self-consistent density functional theory (DFT-GGA, PW91) calculations are used to study the reaction mechanism for nitric oxide (NO) reduction by hydrogen (H 2) on Pt(100). Energetics of various N–O activation paths, including both direct and hydrogen-assisted N–O bond-breaking paths, and the formation of three different N-containing products (N 2, N 2O, and NH3), are systematically studied. On the basis of our analysis, NO* dissociation has a lower barrier than NO* hydrogenation to HNO* or NOH*, and therefore, the direct NO dissociation path is predicted to dominate N–O activation on clean Pt(100). The reaction of atomic N* with N* andmore » NO* is proposed as the mechanism for N 2 and N 2O formation, respectively. NH 3 formation from N* via three successive hydrogenation steps is also studied and is found to be kinetically more difficult than N 2 and N 2O formation from N*. Finally, NO adsorption phase diagrams on Pt(100) are constructed, and these phase diagrams suggest that, at low temperatures (e.g., 400 K), the Pt(100) surface may be covered by half a monolayer of NO. We propose that high NO coverage might affect the NO + H 2 reaction mechanism, and therefore, one should explicitly take the NO coverage into consideration in first-principles studies to determine the reaction mechanism on catalyst surfaces under reaction conditions. In conclusion, a detailed analysis of high NO coverage effects on the reaction mechanism will be presented in a separate contribution.« less

New chemical sources of energy: A theoretical study

NASA Astrophysics Data System (ADS)

Chaban, Galina

The research presented in this dissertation employs methods of quantum chemistry for the search of highly energetic chemical compounds that can have applications as possible energy sources. The areas of research include: (1) improvement of orbital optimization methods for different types of wavefunctions which leads to substantial savings of computer time and memory; (2) predicting new high energy isomers for singlet and triplet states of Nsb3F and their kinetic stability with respect to isomerisation and dissociation reactions; (3) estimation of minimum energy reaction paths for dissociation reactions of high energy isomers of Nsb2Osb2 including potential energy barriers and minimum energy crossing points between the closest singlet and triplet states; (4) investigation of thermodynamic and kinetic stability of Van der Waals complexes M-Hsb2 (M = Li, Be, B, C, Na, Mg, Al, Si) that can play an important role in improvement of energetic properties of hydrogen based rocket fuels; (5) mapping of the potential energy surface for AlHsb2 compound in the region of crossing between sp2Bsb2 and sp2Asb1 electronic states and predicting the kinetic stability of Al complex, which suggests that Al may be among the promising candidates for inclusion into solid hydrogen for the purpose of energy storage.

Autonomous Control Modes and Optimized Path Guidance for Shipboard Landing in High Sea States

DTIC Science & Technology

2016-08-12

Performing Organization: The Pennsylvania State University Department of Aerospace Engineering 231C Hammond Building University Park, PA 16802 Attn...Plant Models Used in the Study The H-60 class model was developed and distributed by ART to both NAVAIR and Penn State research teams. The model...To) 07 109 I 201 4 tD 07 I 08 12016 ’t TITLE AND SUBTITLE Autonomous Control Modes and Optimized Path Guidance for Shipboard Landing in High Sea States

Autonomous Control Modes and Optimized Path Guidance for Shipboard Landing in High Sea States

DTIC Science & Technology

2017-04-15

50 0 50 Singular Values Frequency (rad/s) S in g u la r V a lu e s ( d B ) controller . The non -output variables can be estimated by reliable linear...Contract # N00014-14-C-0004 Autonomous Control Modes and Optimized Path Guidance for Shipboard Landing in High Sea States Progress Report...recovery of a VTOL UAV. There is a clear need for additional levels of stability and control augmentation and, ultimately, fully autonomous landing

Maximal Sensitive Dependence and the Optimal Path to Epidemic Extinction

DTIC Science & Technology

2010-01-01

1996; Elgart and Kamenev, 2004). Instead, in this article, we will employ an eikonal approximation to recast the problem in terms of an effective...a control strategy on the extinction rate can be determined by its effect on the optimal path (Dykman et al., 2008). Through the use of the eikonal ...the solution of Eqs. (6a)–(6b) in the eikonal form (Elgart and Kamenev, 2004; Doering et al., 2005; Kubo et al., 1973; Wentzell, 1976; Gang, 1987

Optimizing Chemical Reactions with Deep Reinforcement Learning.

PubMed

Zhou, Zhenpeng; Li, Xiaocheng; Zare, Richard N

2017-12-27

Deep reinforcement learning was employed to optimize chemical reactions. Our model iteratively records the results of a chemical reaction and chooses new experimental conditions to improve the reaction outcome. This model outperformed a state-of-the-art blackbox optimization algorithm by using 71% fewer steps on both simulations and real reactions. Furthermore, we introduced an efficient exploration strategy by drawing the reaction conditions from certain probability distributions, which resulted in an improvement on regret from 0.062 to 0.039 compared with a deterministic policy. Combining the efficient exploration policy with accelerated microdroplet reactions, optimal reaction conditions were determined in 30 min for the four reactions considered, and a better understanding of the factors that control microdroplet reactions was reached. Moreover, our model showed a better performance after training on reactions with similar or even dissimilar underlying mechanisms, which demonstrates its learning ability.

Epidemic extinction paths in complex networks

NASA Astrophysics Data System (ADS)

Hindes, Jason; Schwartz, Ira B.

2017-05-01

We study the extinction of long-lived epidemics on finite complex networks induced by intrinsic noise. Applying analytical techniques to the stochastic susceptible-infected-susceptible model, we predict the distribution of large fluctuations, the most probable or optimal path through a network that leads to a disease-free state from an endemic state, and the average extinction time in general configurations. Our predictions agree with Monte Carlo simulations on several networks, including synthetic weighted and degree-distributed networks with degree correlations, and an empirical high school contact network. In addition, our approach quantifies characteristic scaling patterns for the optimal path and distribution of large fluctuations, both near and away from the epidemic threshold, in networks with heterogeneous eigenvector centrality and degree distributions.

Epidemic extinction paths in complex networks.

PubMed

Hindes, Jason; Schwartz, Ira B

2017-05-01

We study the extinction of long-lived epidemics on finite complex networks induced by intrinsic noise. Applying analytical techniques to the stochastic susceptible-infected-susceptible model, we predict the distribution of large fluctuations, the most probable or optimal path through a network that leads to a disease-free state from an endemic state, and the average extinction time in general configurations. Our predictions agree with Monte Carlo simulations on several networks, including synthetic weighted and degree-distributed networks with degree correlations, and an empirical high school contact network. In addition, our approach quantifies characteristic scaling patterns for the optimal path and distribution of large fluctuations, both near and away from the epidemic threshold, in networks with heterogeneous eigenvector centrality and degree distributions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khinkis, Mark J.; Kozlov, Aleksandr P.

A radiant, non-catalytic recuperative reformer has a flue gas flow path for conducting hot exhaust gas from a thermal process and a reforming mixture flow path for conducting a reforming mixture. At least a portion of the reforming mixture flow path is positioned adjacent to the flue gas flow path to permit heat transfer from the hot exhaust gas to the reforming mixture. The reforming mixture flow path contains substantially no material commonly used as a catalyst for reforming hydrocarbon fuel (e.g., nickel oxide, platinum group elements or rhenium), but instead the reforming mixture is reformed into a higher calorificmore » fuel via reactions due to the heat transfer and residence time. In a preferred embodiment, a portion of the reforming mixture flow path is positioned outside of flue gas flow path for a relatively large residence time.« less

Air Vehicle Path Planning

DTIC Science & Technology

2001-12-13

6-18 6.13. Apollonius Circle for the Case of Two Unequal Power Radars . . . 6-20 6.14. Solution Triangle...Voronoi edge is an Apollonius circle [32, 19]. In this section, we are concerned with the optimality of the Voronoi path for the two radar exposure...Comparison of Cost vs. Path Length for Constrained Trajectories Around and Between Two Radars 6-18 from the two radars is an Apollonius circle

Fundamental research in the area of high temperature fuel cells in Russia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dyomin, A.K.

1996-04-01

Research in the area of molten carbonate and solid oxide fuel cells has been conducted in Russia since the late 60`s. Institute of High Temperature Electrochemistry is the lead organisation in this area. Research in the area of materials used in fuel cells has allowed us to identify compositions of electrolytes, electrodes, current paths and transmitting, sealing and structural materials appropriate for long-term fuel cell applications. Studies of electrode processes resulted in better understanding of basic patterns of electrode reactions and in the development of a foundation for electrode structure optimization. We have developed methods to increase electrode activity levelsmore » that allowed us to reach current density levels of up to 1 amper/cm{sup 2}. Development of mathematical models of processes in high temperature fuel cells has allowed us to optimize their structure. The results of fundamental studies have been tested on laboratory mockups. MCFC mockups with up to 100 W capacity and SOFC mockups with up to 1 kW capacity have been manufactured and tested at IHTE. There are three SOFC structural options: tube, plate and modular.« less

Ultrafast electron crystallography of the cooperative reaction path in vanadium dioxide

PubMed Central

Yang, Ding-Shyue; Baum, Peter; Zewail, Ahmed H.

2016-01-01

Time-resolved electron diffraction with atomic-scale spatial and temporal resolution was used to unravel the transformation pathway in the photoinduced structural phase transition of vanadium dioxide. Results from bulk crystals and single-crystalline thin-films reveal a common, stepwise mechanism: First, there is a femtosecond V−V bond dilation within 300 fs, second, an intracell adjustment in picoseconds and, third, a nanoscale shear motion within tens of picoseconds. Experiments at different ambient temperatures and pump laser fluences reveal a temperature-dependent excitation threshold required to trigger the transitional reaction path of the atomic motions. PMID:27376103

Laser cutting with chemical reaction assist

DOEpatents

Gettemy, Donald J.

1992-01-01

A method for cutting with a laser beam where an oxygen-hydrocarbon reaction is used to provide auxiliary energy to a metal workpiece to supplement the energy supplied by the laser. Oxygen is supplied to the laser focus point on the workpiece by a nozzle through which the laser beam also passes. A liquid hydrocarbon is supplied by coating the workpiece along the cutting path with the hydrocarbon prior to laser irradiation or by spraying a stream of hydrocarbon through a nozzle aimed at a point on the cutting path which is just ahead of the focus point during irradiation.

Laser cutting with chemical reaction assist

DOEpatents

Gettemy, D.J.

1992-11-17

A method is described for cutting with a laser beam where an oxygen-hydrocarbon reaction is used to provide auxiliary energy to a metal workpiece to supplement the energy supplied by the laser. Oxygen is supplied to the laser focus point on the workpiece by a nozzle through which the laser beam also passes. A liquid hydrocarbon is supplied by coating the workpiece along the cutting path with the hydrocarbon prior to laser irradiation or by spraying a stream of hydrocarbon through a nozzle aimed at a point on the cutting path which is just ahead of the focus point during irradiation. 1 figure.

Effect of Electronic Excitation on Hydrogen Atom Transfer (Tautomerization) Reactions for the DNA Base Adenine

NASA Technical Reports Server (NTRS)

Chaban, Galina M.; Salter, Latasha M.; Kwak, Dochan (Technical Monitor)

2002-01-01

Geometrical structures and energetic properties for four different tautomers of adenine are calculated in this study, using multi-configurational wave functions. Both the ground and the lowest single excited state potential energy surface are studied. The energetic order of the tautomers on the ground state potential surface is 9H less than 7H less than 3H less than 1H, while on the excited state surface this order is found to be different: 3H less than 1H less than 9H less than 7H. Minimum energy reaction paths are obtained for hydrogen atom transfer (9 yields 3 tautomerization) reactions in the ground and the lowest excited electronic state. It is found that the barrier heights and the shapes of the reaction paths are different for the ground and the excited electronic state, suggesting that the probability of such tautomerization reaction is higher on the excited state potential energy surface. The barrier for this reaction in the excited state may become very low in the presence of water or other polar solvent molecules, and therefore such tautomerization reaction may play an important role in the solution phase photochemistry of adenine.

Optimizing the Compressive Strength of Strain-Hardenable Stretch-Formed Microtruss Architectures

NASA Astrophysics Data System (ADS)

Yu, Bosco; Abu Samk, Khaled; Hibbard, Glenn D.

2015-05-01

The mechanical performance of stretch-formed microtrusses is determined by both the internal strut architecture and the accumulated plastic strain during fabrication. The current study addresses the question of optimization, by taking into consideration the interdependency between fabrication path, material properties and architecture. Low carbon steel (AISI1006) and aluminum (AA3003) material systems were investigated experimentally, with good agreement between measured values and the analytical model. The compressive performance of the microtrusses was then optimized on a minimum weight basis under design constraints such as fixed starting sheet thickness and final microtruss height by satisfying the Karush-Kuhn-Tucker condition. The optimization results were summarized as carpet plots in order to meaningfully visualize the interdependency between architecture, microstructural state, and mechanical performance, enabling material and processing path selection.

Optimal short-range trajectories for helicopters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Slater, G.L.; Erzberger, H.

1982-12-01

An optimal flight path algorithm using a simplified altitude state model and a priori climb cruise descent flight profile was developed and applied to determine minimum fuel and minimum cost trajectories for a helicopter flying a fixed range trajectory. In addition, a method was developed for obtaining a performance model in simplified form which is based on standard flight manual data and which is applicable to the computation of optimal trajectories. The entire performance optimization algorithm is simple enough that on line trajectory optimization is feasible with a relatively small computer. The helicopter model used is the Silorsky S-61N. Themore » results show that for this vehicle the optimal flight path and optimal cruise altitude can represent a 10% fuel saving on a minimum fuel trajectory. The optimal trajectories show considerable variability because of helicopter weight, ambient winds, and the relative cost trade off between time and fuel. In general, reasonable variations from the optimal velocities and cruise altitudes do not significantly degrade the optimal cost. For fuel optimal trajectories, the optimum cruise altitude varies from the maximum (12,000 ft) to the minimum (0 ft) depending on helicopter weight.« less

Application of GA, PSO, and ACO algorithms to path planning of autonomous underwater vehicles

NASA Astrophysics Data System (ADS)

Aghababa, Mohammad Pourmahmood; Amrollahi, Mohammad Hossein; Borjkhani, Mehdi

2012-09-01

In this paper, an underwater vehicle was modeled with six dimensional nonlinear equations of motion, controlled by DC motors in all degrees of freedom. Near-optimal trajectories in an energetic environment for underwater vehicles were computed using a numerical solution of a nonlinear optimal control problem (NOCP). An energy performance index as a cost function, which should be minimized, was defined. The resulting problem was a two-point boundary value problem (TPBVP). A genetic algorithm (GA), particle swarm optimization (PSO), and ant colony optimization (ACO) algorithms were applied to solve the resulting TPBVP. Applying an Euler-Lagrange equation to the NOCP, a conjugate gradient penalty method was also adopted to solve the TPBVP. The problem of energetic environments, involving some energy sources, was discussed. Some near-optimal paths were found using a GA, PSO, and ACO algorithms. Finally, the problem of collision avoidance in an energetic environment was also taken into account.

Optimizing Chemical Reactions with Deep Reinforcement Learning

PubMed Central

2017-01-01

Deep reinforcement learning was employed to optimize chemical reactions. Our model iteratively records the results of a chemical reaction and chooses new experimental conditions to improve the reaction outcome. This model outperformed a state-of-the-art blackbox optimization algorithm by using 71% fewer steps on both simulations and real reactions. Furthermore, we introduced an efficient exploration strategy by drawing the reaction conditions from certain probability distributions, which resulted in an improvement on regret from 0.062 to 0.039 compared with a deterministic policy. Combining the efficient exploration policy with accelerated microdroplet reactions, optimal reaction conditions were determined in 30 min for the four reactions considered, and a better understanding of the factors that control microdroplet reactions was reached. Moreover, our model showed a better performance after training on reactions with similar or even dissimilar underlying mechanisms, which demonstrates its learning ability. PMID:29296675

Upconverting nanoparticles for optimizing scintillator based detection systems

DOEpatents

Kross, Brian; McKisson, John E; McKisson, John; Weisenberger, Andrew; Xi, Wenze; Zom, Carl

2013-09-17

An upconverting device for a scintillation detection system is provided. The detection system comprises a scintillator material, a sensor, a light transmission path between the scintillator material and the sensor, and a plurality of upconverting nanoparticles particles positioned in the light transmission path.

Conception et analyse d'un systeme d'optimisation de plans de vol pour les avions

NASA Astrophysics Data System (ADS)

Maazoun, Wissem

The main objective of this thesis is to develop an optimization method for the preparation of flight plans for aircrafts. The flight plan minimizes all costs associated with the flight. We determine an optimal path for an airplane from a departure airport to a destination airport. The optimal path minimizes the sum of all costs, i.e. the cost of fuel added to the cost of time (wages, rental of the aircraft, arrival delays, etc.). The optimal trajectory is obtained by considering all possible trajectories on a 3D graph (longitude, latitude and altitude) where the altitude levels are separated by 2,000 feet, and by applying a shortest path algorithm. The main task was to accurately compute fuel consumption on each edge of the graph, making sure that each arc has a minimal cost and is covered in a realistic way from the point of view of control, i.e. in accordance with the rules of navigation. To compute the cost of an arc, we take into account weather conditions (temperature, pressure, wind components, etc.). The optimization of each arc is done via the evaluation of an optimum speed that takes all costs into account. Each arc of the graph typically includes several sub-phases of the flight, e.g. altitude change, speed change, and constant speed and altitude. In the initial climb and the final descent phases, the costs are determined by considering altitude changes at constant CAS (Calibrated Air Speed) or constant Mach number. CAS and Mach number are adjusted to minimize cost. The aerodynamic model used is the one proposed by Eurocontrol, which uses the BADA (Base of Aircraft Data) tables. This model is based on the total energy equation that determines the instantaneous fuel consumption. Calculations on each arc are done by solving a system of differential equations that systematically takes all costs into account. To compute the cost of an arc, we must know the time to go through it, which is generally unknown. To have well-posed boundary conditions, we use the horizontal displacement as the independent variable of the system of differential equations. We consider the velocity components of the wind in a 3D system of coordinates to compute the instantaneous ground speed of the aircraft. To consider the cost of time, we use the cost index. The cost of an arc depends on the aircraft mass at the beginning of this arc, and this mass depends on the path. As we consider all possible paths, the cost of an arc must be computed for each trajectory to which it belongs. For a long-distance flight, the number of arcs to be considered in the graph is large and therefore the cost of an arc is typically computed many times. Our algorithm computes the costs of one million arcs in seconds while having a high accuracy. The determination of the optimal trajectory can therefore be done in a short time. To get the optimal path, the mass of the aircraft at the departure point must also be optimal. It is therefore necessary to know the optimal amount of fuel for the journey. The aircraft mass is known only at the arrival point. This mass is the mass of the aircraft including passengers, cargo and reserve fuel mass. The optimal path is determined by calculating backwards, i.e. from the arrival point to the departure point. For the determination of the optimal trajectory, we use an elliptical grid that has focal points at the departure and arrival points. The use of this grid is essential for the construction of a direct and acyclic graph. We use the Bellman-Ford algorithm on a DAG to determine the shortest path. This algorithm is easy to implement and results in short computation times. Our algorithm computes an optimal trajectory with an optimal cost for each arc. Altitude changes are done optimally with respect to the mass of the aircraft and the cost of time. Our algorithm gives the mass, speed, altitude and total cost at any point of the trajectory as well as the optimal profiles of climb and descent. A prototype has been implemented in C. We made simulations of all types of possible arcs and of several complete trajectories to illustrate the behaviour of the algorithm.

Study on the measuring distance for blood glucose infrared spectral measuring by Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Li, Xiang

2016-10-01

Blood glucose monitoring is of great importance for controlling diabetes procedure and preventing the complications. At present, the clinical blood glucose concentration measurement is invasive and could be replaced by noninvasive spectroscopy analytical techniques. Among various parameters of optical fiber probe used in spectrum measuring, the measurement distance is the key one. The Monte Carlo technique is a flexible method for simulating light propagation in tissue. The simulation is based on the random walks that photons make as they travel through tissue, which are chosen by statistically sampling the probability distributions for step size and angular deflection per scattering event. The traditional method for determine the optimal distance between transmitting fiber and detector is using Monte Carlo simulation to find out the point where most photons come out. But there is a problem. In the epidermal layer there is no artery, vein or capillary vessel. Thus, when photons propagate and interactive with tissue in epidermal layer, no information is given to the photons. A new criterion is proposed to determine the optimal distance, which is named effective path length in this paper. The path length of each photons travelling in dermis is recorded when running Monte-Carlo simulation, which is the effective path length defined above. The sum of effective path length of every photon at each point is calculated. The detector should be place on the point which has most effective path length. Then the optimal measuring distance between transmitting fiber and detector is determined.

Shortest multiple disconnected path for the analysis of entanglements in two- and three-dimensional polymeric systems

NASA Astrophysics Data System (ADS)

Kröger, Martin

2005-06-01

We present an algorithm which returns a shortest path and related number of entanglements for a given configuration of a polymeric system in 2 or 3 dimensions. Rubinstein and Helfand, and later Everaers et al. introduced a concept to extract primitive paths for dense polymeric melts made of linear chains (a multiple disconnected multibead 'path'), where each primitive path is defined as a path connecting the (space-fixed) ends of a polymer under the constraint of non-interpenetration (excluded volume) between primitive paths of different chains, such that the multiple disconnected path fulfills a minimization criterion. The present algorithm uses geometrical operations and provides a—model independent—efficient approximate solution to this challenging problem. Primitive paths are treated as 'infinitely' thin (we further allow for finite thickness to model excluded volume), and tensionless lines rather than multibead chains, excluded volume is taken into account without a force law. The present implementation allows to construct a shortest multiple disconnected path (SP) for 2D systems (polymeric chain within spherical obstacles) and an optimal SP for 3D systems (collection of polymeric chains). The number of entanglements is then simply obtained from the SP as either the number of interior kinks, or from the average length of a line segment. Further, information about structure and potentially also the dynamics of entanglements is immediately available from the SP. We apply the method to study the 'concentration' dependence of the degree of entanglement in phantom chain systems. Program summaryTitle of program:Z Catalogue number:ADVG Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADVG Program obtainable from: CPC Program Library, Queen's University of Belfast, N. Ireland Computer for which the program is designed and others on which it has been tested: Silicon Graphics (Irix), Sun (Solaris), PC (Linux) Operating systems or monitors under which the program has been tested: UNIX, Linux Program language used: USANSI Fortran 77 and Fortran 90 Memory required to execute with typical data: 1 MByte No. of lines in distributed program, including test data, etc.: 10 660 No. of bytes in distributed program, including test data, etc.: 119 551 Distribution formet:tar.gz Nature of physical problem: The problem is to obtain primitive paths substantiating a shortest multiple disconnected path (SP) for a given polymer configuration (chains of particles, with or without additional single particles as obstacles for the 2D case). Primitive paths are here defined as in [M. Rubinstein, E. Helfand, J. Chem. Phys. 82 (1985) 2477; R. Everaers, S.K. Sukumaran, G.S. Grest, C. Svaneborg, A. Sivasubramanian, K. Kremer, Science 303 (2004) 823] as the shortest line (path) respecting 'topological' constraints (from neighboring polymers or point obstacles) between ends of polymers. There is a unique solution for the 2D case. For the 3D case it is unique if we construct a primitive path of a single chain embedded within fixed line obstacles [J.S.B. Mitchell, Geometric shortest paths and network optimization, in: J.-R. Sack, J. Urrutia (Eds.), Handbook of Computational Geometry, Elsevier, Amsterdam, 2000, pp. 633-701]. For a large 3D configuration made of several chains, short is meant to be the Euclidean shortest multiple disconnected path (SP) where primitive paths are constructed for all chains simultaneously. While the latter problem, in general, does not possess a unique solution, the algorithm must return a locally optimal solution, robust against minor displacements of the disconnected path and chain re-labeling. The problem is solved if the number of kinks (or entanglements Z), explicitly deduced from the SP, is quite insensitive to the exact conformation of the SP which allows to estimate Z with a small error. Efficient method of solution: Primitive paths are constructed from the given polymer configuration (a non-shortest multiple disconnected path, including obstacles, if present) by first replacing each polymer contour by a line with a number of 'kinks' (beads, nodes) and 'segments' (edges). To obtain primitive paths, defined to be uncrossable by any other objects (neighboring primitive paths, line or point obstacles), the algorithm minimizes the length of all primitive paths consecutively, until a final minimum Euclidean length of the SP is reached. Fast geometric operations rather than dynamical methods are used to minimize the contour lengths of the primitive paths. Neighbor lists are used to keep track of potentially intersecting segments of other chains. Periodic boundary conditions are employed. A finite small line thickness is used in order to make sure that entanglements are not 'lost' due to finite precision of representation of numbers. Restrictions on the complexity of the problem: For a single chain embedded within fixed line or point obstacles, the algorithm returns the exact SP. For more complex problems, the algorithm returns a locally optimal SP. Except for exotic, probably rare, configurations it turns out that different locally optimal SPs possess quite an identical number of nodes. In general, the problem constructing the SP is known to be NP-hard [J.S.B. Mitchell, Geometric shortest paths and network optimization, in: J.-R. Sack, J. Urrutia (Eds.), Handbook of Computational Geometry, Elsevier, Amsterdam, 2000, pp. 633-701], and we offer a solution which should suffice to analyze physical problems, and gives an estimate about the precision and uniqueness of the result (from a standard deviation by varying the parameter: cyclicswitch). The program is NOT restricted to handle systems for which segment lengths of the SP exceed half the box size. Typical running time: Typical running times are approximately two orders of magnitude shorter compared with the ones needed for a corresponding molecular dynamics approach, and scale mostly linearly with system size. We provide a benchmark table.

Optimization of a high-yield, low-areal-density fusion product source at the National Ignition Facility with applications in nucleosynthesis experiments

NASA Astrophysics Data System (ADS)

Gatu Johnson, M.; Casey, D. T.; Hohenberger, M.; Zylstra, A. B.; Bacher, A.; Brune, C. R.; Bionta, R. M.; Craxton, R. S.; Ellison, C. L.; Farrell, M.; Frenje, J. A.; Garbett, W.; Garcia, E. M.; Grim, G. P.; Hartouni, E.; Hatarik, R.; Herrmann, H. W.; Hohensee, M.; Holunga, D. M.; Hoppe, M.; Jackson, M.; Kabadi, N.; Khan, S. F.; Kilkenny, J. D.; Kohut, T. R.; Lahmann, B.; Le, H. P.; Li, C. K.; Masse, L.; McKenty, P. W.; McNabb, D. P.; Nikroo, A.; Parham, T. G.; Parker, C. E.; Petrasso, R. D.; Pino, J.; Remington, B.; Rice, N. G.; Rinderknecht, H. G.; Rosenberg, M. J.; Sanchez, J.; Sayre, D. B.; Schoff, M. E.; Shuldberg, C. M.; Séguin, F. H.; Sio, H.; Walters, Z. B.; Whitley, H. D.

2018-05-01

Polar-direct-drive exploding pushers are used as a high-yield, low-areal-density fusion product source at the National Ignition Facility with applications including diagnostic calibration, nuclear security, backlighting, electron-ion equilibration, and nucleosynthesis-relevant experiments. In this paper, two different paths to improving the performance of this platform are explored: (i) optimizing the laser drive, and (ii) optimizing the target. While the present study is specifically geared towards nucleosynthesis experiments, the results are generally applicable. Example data from T2/3He-gas-filled implosions with trace deuterium are used to show that yield and ion temperature (Tion) from 1.6 mm-outer-diameter thin-glass-shell capsule implosions are improved at a set laser energy by switching from a ramped to a square laser pulse shape, and that increased laser energy further improves yield and Tion, although by factors lower than predicted by 1 D simulations. Using data from D2/3He-gas-filled implosions, yield at a set Tion is experimentally verified to increase with capsule size. Uniform D3He-proton spectra from 3 mm-outer-diameter CH shell implosions demonstrate the utility of this platform for studying charged-particle-producing reactions relevant to stellar nucleosynthesis.

Optimization of a high-yield, low-areal-density fusion product source at the National Ignition Facility with applications in nucleosynthesis experiments

DOE PAGES

Gatu Johnson, M.; Casey, D. T.; Hohenberger, M.; ...

2018-05-09

Polar-direct-drive exploding pushers are used as a high-yield, low-areal-density fusion product source at the National Ignition Facility with applications including diagnostic calibration, nuclear security, backlighting, electron-ion equilibration, and nucleosynthesis-relevant experiments. In this paper, two different paths to improving the performance of this platform are explored: (i) optimizing the laser drive, and (ii) optimizing the target. While the present study is specifically geared towards nucleosynthesis experiments, the results are generally applicable. Example data from T 2/ 3He-gas-filled implosions with trace deuterium are used to show that yield and ion temperature (Tion) from 1.6 mm-outer-diameter thin-glass-shell capsule implosions are improved at amore » set laser energy by switching from a ramped to a square laser pulse shape, and that increased laser energy further improves yield and Tion, although by factors lower than predicted by 1 D simulations. Using data from D2-3He-gas-filled implosions, yield at a set Tion is experimentally verified to increase with capsule size. Uniform D-3He-proton spectra from 3 mm-outer-diameter CH shell implosions demonstrate the utility of this platform for studying charged-particle-producing reactions relevant to stellar nucleosynthesis.« less

Optimization of a high-yield, low-areal-density fusion product source at the National Ignition Facility with applications in nucleosynthesis experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gatu Johnson, M.; Casey, D. T.; Hohenberger, M.

Polar-direct-drive exploding pushers are used as a high-yield, low-areal-density fusion product source at the National Ignition Facility with applications including diagnostic calibration, nuclear security, backlighting, electron-ion equilibration, and nucleosynthesis-relevant experiments. In this paper, two different paths to improving the performance of this platform are explored: (i) optimizing the laser drive, and (ii) optimizing the target. While the present study is specifically geared towards nucleosynthesis experiments, the results are generally applicable. Example data from T 2/ 3He-gas-filled implosions with trace deuterium are used to show that yield and ion temperature (Tion) from 1.6 mm-outer-diameter thin-glass-shell capsule implosions are improved at amore » set laser energy by switching from a ramped to a square laser pulse shape, and that increased laser energy further improves yield and Tion, although by factors lower than predicted by 1 D simulations. Using data from D2-3He-gas-filled implosions, yield at a set Tion is experimentally verified to increase with capsule size. Uniform D-3He-proton spectra from 3 mm-outer-diameter CH shell implosions demonstrate the utility of this platform for studying charged-particle-producing reactions relevant to stellar nucleosynthesis.« less

Optimization of Supersonic Transport Trajectories

NASA Technical Reports Server (NTRS)

Ardema, Mark D.; Windhorst, Robert; Phillips, James

1998-01-01

This paper develops a near-optimal guidance law for generating minimum fuel, time, or cost fixed-range trajectories for supersonic transport aircraft. The approach uses a choice of new state variables along with singular perturbation techniques to time-scale decouple the dynamic equations into multiple equations of single order (second order for the fast dynamics). Application of the maximum principle to each of the decoupled equations, as opposed to application to the original coupled equations, avoids the two point boundary value problem and transforms the problem from one of a functional optimization to one of multiple function optimizations. It is shown that such an approach produces well known aircraft performance results such as minimizing the Brequet factor for minimum fuel consumption and the energy climb path. Furthermore, the new state variables produce a consistent calculation of flight path angle along the trajectory, eliminating one of the deficiencies in the traditional energy state approximation. In addition, jumps in the energy climb path are smoothed out by integration of the original dynamic equations at constant load factor. Numerical results performed for a supersonic transport design show that a pushover dive followed by a pullout at nominal load factors are sufficient maneuvers to smooth the jump.

Optimized path planning for soft tissue resection via laser vaporization

NASA Astrophysics Data System (ADS)

Ross, Weston; Cornwell, Neil; Tucker, Matthew; Mann, Brian; Codd, Patrick

2018-02-01

Robotic and robotic-assisted surgeries are becoming more prevalent with the promise of improving surgical outcomes through increased precision, reduced operating times, and minimally invasive procedures. The handheld laser scalpel in neurosurgery has been shown to provide a more gentle approach to tissue manipulation on or near critical structures over classical tooling, though difficulties of control have prevented large scale adoption of the tool. This paper presents a novel approach to generating a cutting path for the volumetric resection of tissue using a computer-guided laser scalpel. A soft tissue ablation simulator is developed and used in conjunction with an optimization routine to select parameters which maximize the total resection of target tissue while minimizing the damage to surrounding tissue. The simulator predicts the ablative properties of tissue from an interrogation cut for tuning and simulates the removal of a tumorous tissue embedded on the surface of healthy tissue using a laser scalpel. We demonstrate the ability to control depth and smoothness of cut using genetic algorithms to optimize the ablation parameters and cutting path. The laser power level, cutting rate and spacing between cuts are optimized over multiple surface cuts to achieve the desired resection volumes.

Social Milieu Oriented Routing: A New Dimension to Enhance Network Security in WSNs.

PubMed

Liu, Lianggui; Chen, Li; Jia, Huiling

2016-02-19

In large-scale wireless sensor networks (WSNs), in order to enhance network security, it is crucial for a trustor node to perform social milieu oriented routing to a target a trustee node to carry out trust evaluation. This challenging social milieu oriented routing with more than one end-to-end Quality of Trust (QoT) constraint has proved to be NP-complete. Heuristic algorithms with polynomial and pseudo-polynomial-time complexities are often used to deal with this challenging problem. However, existing solutions cannot guarantee the efficiency of searching; that is, they can hardly avoid obtaining partial optimal solutions during a searching process. Quantum annealing (QA) uses delocalization and tunneling to avoid falling into local minima without sacrificing execution time. This has been proven a promising way to many optimization problems in recently published literatures. In this paper, for the first time, with the help of a novel approach, that is, configuration path-integral Monte Carlo (CPIMC) simulations, a QA-based optimal social trust path (QA_OSTP) selection algorithm is applied to the extraction of the optimal social trust path in large-scale WSNs. Extensive experiments have been conducted, and the experiment results demonstrate that QA_OSTP outperforms its heuristic opponents.

Optimal symmetric flight with an intermediate vehicle model

NASA Technical Reports Server (NTRS)

Menon, P. K. A.; Kelley, H. J.; Cliff, E. M.

1983-01-01

Optimal flight in the vertical plane with a vehicle model intermediate in complexity between the point-mass and energy models is studied. Flight-path angle takes on the role of a control variable. Range-open problems feature subarcs of vertical flight and singular subarcs. The class of altitude-speed-range-time optimization problems with fuel expenditure unspecified is investigated and some interesting phenomena uncovered. The maximum-lift-to-drag glide appears as part of the family, final-time-open, with appropriate initial and terminal transient exceeding level-flight drag, some members exhibiting oscillations. Oscillatory paths generally fail the Jacobi test for durations exceeding a period and furnish a minimum only for short-duration problems.

Sampling-Based Coverage Path Planning for Complex 3D Structures

DTIC Science & Technology

2012-09-01

one such task, in which a single robot must sweep its end effector over the entirety of a known workspace. For two-dimensional environments, optimal...structures. First, we introduce a new algorithm for planning feasible coverage paths. It is more computationally efficient in problems of complex geometry...iteratively shortens and smooths a feasible coverage path; robot configurations are adjusted without violating any coverage con- straints. Third, we propose

Application of ant colony algorithm in path planning of the data center room robot

NASA Astrophysics Data System (ADS)

Wang, Yong; Ma, Jianming; Wang, Ying

2017-05-01

According to the Internet Data Center (IDC) room patrol robot as the background, the robot in the search path of autonomous obstacle avoidance and path planning ability, worked out in advance of the robot room patrol mission. The simulation experimental results show that the improved ant colony algorithm for IDC room patrol robot obstacle avoidance planning, makes the robot along an optimal or suboptimal and safe obstacle avoidance path to reach the target point to complete the task. To prove the feasibility of the method.

Solving fuzzy shortest path problem by genetic algorithm

NASA Astrophysics Data System (ADS)

Syarif, A.; Muludi, K.; Adrian, R.; Gen, M.

2018-03-01

Shortest Path Problem (SPP) is known as one of well-studied fields in the area Operations Research and Mathematical Optimization. It has been applied for many engineering and management designs. The objective is usually to determine path(s) in the network with minimum total cost or traveling time. In the past, the cost value for each arc was usually assigned or estimated as a deteministic value. For some specific real world applications, however, it is often difficult to determine the cost value properly. One way of handling such uncertainty in decision making is by introducing fuzzy approach. With this situation, it will become difficult to solve the problem optimally. This paper presents the investigations on the application of Genetic Algorithm (GA) to a new SPP model in which the cost values are represented as Triangular Fuzzy Number (TFN). We adopts the concept of ranking fuzzy numbers to determine how good the solutions. Here, by giving his/her degree value, the decision maker can determine the range of objective value. This would be very valuable for decision support system in the real world applications.Simulation experiments were carried out by modifying several test problems with 10-25 nodes. It is noted that the proposed approach is capable attaining a good solution with different degree of optimism for the tested problems.

Interpolating between random walks and optimal transportation routes: Flow with multiple sources and targets

NASA Astrophysics Data System (ADS)

Guex, Guillaume

2016-05-01

In recent articles about graphs, different models proposed a formalism to find a type of path between two nodes, the source and the target, at crossroads between the shortest-path and the random-walk path. These models include a freely adjustable parameter, allowing to tune the behavior of the path toward randomized movements or direct routes. This article presents a natural generalization of these models, namely a model with multiple sources and targets. In this context, source nodes can be viewed as locations with a supply of a certain good (e.g. people, money, information) and target nodes as locations with a demand of the same good. An algorithm is constructed to display the flow of goods in the network between sources and targets. With again a freely adjustable parameter, this flow can be tuned to follow routes of minimum cost, thus displaying the flow in the context of the optimal transportation problem or, by contrast, a random flow, known to be similar to the electrical current flow if the random-walk is reversible. Moreover, a source-targetcoupling can be retrieved from this flow, offering an optimal assignment to the transportation problem. This algorithm is described in the first part of this article and then illustrated with case studies.

Homography-based control scheme for mobile robots with nonholonomic and field-of-view constraints.

PubMed

López-Nicolás, Gonzalo; Gans, Nicholas R; Bhattacharya, Sourabh; Sagüés, Carlos; Guerrero, Josechu J; Hutchinson, Seth

2010-08-01

In this paper, we present a visual servo controller that effects optimal paths for a nonholonomic differential drive robot with field-of-view constraints imposed by the vision system. The control scheme relies on the computation of homographies between current and goal images, but unlike previous homography-based methods, it does not use the homography to compute estimates of pose parameters. Instead, the control laws are directly expressed in terms of individual entries in the homography matrix. In particular, we develop individual control laws for the three path classes that define the language of optimal paths: rotations, straight-line segments, and logarithmic spirals. These control laws, as well as the switching conditions that define how to sequence path segments, are defined in terms of the entries of homography matrices. The selection of the corresponding control law requires the homography decomposition before starting the navigation. We provide a controllability and stability analysis for our system and give experimental results.

Effective use of congestion in complex networks

NASA Astrophysics Data System (ADS)

Echagüe, Juan; Cholvi, Vicent; Kowalski, Dariusz R.

2018-03-01

In this paper, we introduce a congestion-aware routing protocol that selects the paths according to the congestion of nodes in the network. The aim is twofold: on one hand, and in order to prevent the networks from collapsing, it provides a good tolerance to nodes' overloads; on the other hand, and in order to guarantee efficient communication, it also incentivize the routes to follow short paths. We analyze the performance of our proposed routing strategy by means of a series of experiments carried out by using simulations. We show that it provides a tolerance to collapse close to the optimal value. Furthermore, the average length of the paths behaves optimally up to the certain value of packet generation rate ρ and it grows in a linear fashion with the increase of ρ.

Optimal guidance with obstacle avoidance for nap-of-the-earth flight

NASA Technical Reports Server (NTRS)

Pekelsma, Nicholas J.

1988-01-01

The development of automatic guidance is discussed for helicopter Nap-of-the-Earth (NOE) and near-NOE flight. It deals with algorithm refinements relating to automated real-time flight path planning and to mission planning. With regard to path planning, it relates rotorcraft trajectory characteristics to the NOE computation scheme and addresses real-time computing issues and both ride quality issues and pilot-vehicle interfaces. The automated mission planning algorithm refinements include route optimization, automatic waypoint generation, interactive applications, and provisions for integrating the results into the real-time path planning software. A microcomputer based mission planning workstation was developed and is described. Further, the application of Defense Mapping Agency (DMA) digital terrain to both the mission planning workstation and to automatic guidance is both discussed and illustrated.

Path-oriented early reaction to approaching disruptions in ASDEX Upgrade and TCV in view of the future needs for ITER and DEMO

NASA Astrophysics Data System (ADS)

Maraschek, M.; Gude, A.; Igochine, V.; Zohm, H.; Alessi, E.; Bernert, M.; Cianfarani, C.; Coda, S.; Duval, B.; Esposito, B.; Fietz, S.; Fontana, M.; Galperti, C.; Giannone, L.; Goodman, T.; Granucci, G.; Marelli, L.; Novak, S.; Paccagnella, R.; Pautasso, G.; Piovesan, P.; Porte, L.; Potzel, S.; Rapson, C.; Reich, M.; Sauter, O.; Sheikh, U.; Sozzi, C.; Spizzo, G.; Stober, J.; Treutterer, W.; ZancaP; ASDEX Upgrade Team; TCV Team; the EUROfusion MST1 Team

2018-01-01

Routine reaction to approaching disruptions in tokamaks is currently largely limited to machine protection by mitigating an ongoing disruption, which remains a basic requirement for ITER and DEMO [1]. Nevertheless, a mitigated disruption still generates stress to the device. Additionally, in future fusion devices, high-performance discharge time itself will be very valuable. Instead of reacting only on generic features, occurring shortly before the disruption, the ultimate goal is to actively avoid approaching disruptions at an early stage, sustain the discharges whenever possible and restrict mitigated disruptions to major failures. Knowledge of the most relevant root causes and the corresponding chain of events leading to disruption, the disruption path, is a prerequisite. For each disruption path, physics-based sensors and adequate actuators must be defined and their limitations considered. Early reaction facilitates the efficiency of the actuators and enhances the probability of a full recovery. Thus, sensors that detect potential disruptions in time are to be identified. Once the entrance into a disruption path is detected, we propose a hierarchy of actions consisting of (I) recovery of the discharge to full performance or at least continuation with a less disruption-prone backup scenario, (II) complete avoidance of disruption to sustain the discharge or at least delay it for a controlled termination and, (III), only as last resort, a disruption mitigation. Based on the understanding of disruption paths, a hierarchical and path-specific handling strategy must be developed. Such schemes, testable in present devices, could serve as guidelines for ITER and DEMO operation. For some disruption paths, experiments have been performed at ASDEX Upgrade and TCV. Disruptions were provoked in TCV by impurity injection into ELMy H-mode discharges and in ASDEX Upgrade by forcing a density limit in H-mode discharges. The new approach proposed in this paper is discussed for these cases. For the H-mode density limit sensors used so far react too late. Thus a plasma-state boundary is proposed, that can serve as an adequate early sensor for avoiding density limit disruptions in H-modes and for recovery to full performance.

Tool path strategy and cutting process monitoring in intelligent machining

NASA Astrophysics Data System (ADS)

Chen, Ming; Wang, Chengdong; An, Qinglong; Ming, Weiwei

2018-06-01

Intelligent machining is a current focus in advanced manufacturing technology, and is characterized by high accuracy and efficiency. A central technology of intelligent machining—the cutting process online monitoring and optimization—is urgently needed for mass production. In this research, the cutting process online monitoring and optimization in jet engine impeller machining, cranio-maxillofacial surgery, and hydraulic servo valve deburring are introduced as examples of intelligent machining. Results show that intelligent tool path optimization and cutting process online monitoring are efficient techniques for improving the efficiency, quality, and reliability of machining.

Simulation in production of open rotor propellers: from optimal surface geometry to automated control of mechanical treatment

NASA Astrophysics Data System (ADS)

Grinyok, A.; Boychuk, I.; Perelygin, D.; Dantsevich, I.

2018-03-01

A complex method of the simulation and production design of open rotor propellers was studied. An end-to-end diagram was proposed for the evaluating, designing and experimental testing the optimal geometry of the propeller surface, for the machine control path generation as well as for simulating the cutting zone force condition and its relationship with the treatment accuracy which was defined by the propeller elastic deformation. The simulation data provided the realization of the combined automated path control of the cutting tool.

Multiscale simulations of patchy particle systems combining Molecular Dynamics, Path Sampling and Green's Function Reaction Dynamics

NASA Astrophysics Data System (ADS)

Bolhuis, Peter

Important reaction-diffusion processes, such as biochemical networks in living cells, or self-assembling soft matter, span many orders in length and time scales. In these systems, the reactants' spatial dynamics at mesoscopic length and time scales of microns and seconds is coupled to the reactions between the molecules at microscopic length and time scales of nanometers and milliseconds. This wide range of length and time scales makes these systems notoriously difficult to simulate. While mean-field rate equations cannot describe such processes, the mesoscopic Green's Function Reaction Dynamics (GFRD) method enables efficient simulation at the particle level provided the microscopic dynamics can be integrated out. Yet, many processes exhibit non-trivial microscopic dynamics that can qualitatively change the macroscopic behavior, calling for an atomistic, microscopic description. The recently developed multiscale Molecular Dynamics Green's Function Reaction Dynamics (MD-GFRD) approach combines GFRD for simulating the system at the mesocopic scale where particles are far apart, with microscopic Molecular (or Brownian) Dynamics, for simulating the system at the microscopic scale where reactants are in close proximity. The association and dissociation of particles are treated with rare event path sampling techniques. I will illustrate the efficiency of this method for patchy particle systems. Replacing the microscopic regime with a Markov State Model avoids the microscopic regime completely. The MSM is then pre-computed using advanced path-sampling techniques such as multistate transition interface sampling. I illustrate this approach on patchy particle systems that show multiple modes of binding. MD-GFRD is generic, and can be used to efficiently simulate reaction-diffusion systems at the particle level, including the orientational dynamics, opening up the possibility for large-scale simulations of e.g. protein signaling networks.

Simulating biochemical physics with computers: 1. Enzyme catalysis by phosphotriesterase and phosphodiesterase; 2. Integration-free path-integral method for quantum-statistical calculations

NASA Astrophysics Data System (ADS)

Wong, Kin-Yiu

We have simulated two enzymatic reactions with molecular dynamics (MD) and combined quantum mechanical/molecular mechanical (QM/MM) techniques. One reaction is the hydrolysis of the insecticide paraoxon catalyzed by phosphotriesterase (PTE). PTE is a bioremediation candidate for environments contaminated by toxic nerve gases (e.g., sarin) or pesticides. Based on the potential of mean force (PMF) and the structural changes of the active site during the catalysis, we propose a revised reaction mechanism for PTE. Another reaction is the hydrolysis of the second-messenger cyclic adenosine 3'-5'-monophosphate (cAMP) catalyzed by phosphodiesterase (PDE). Cyclicnucleotide PDE is a vital protein in signal-transduction pathways and thus a popular target for inhibition by drugs (e.g., ViagraRTM). A two-dimensional (2-D) free-energy profile has been generated showing that the catalysis by PDE proceeds in a two-step SN2-type mechanism. Furthermore, to characterize a chemical reaction mechanism in experiment, a direct probe is measuring kinetic isotope effects (KIEs). KIEs primarily arise from internuclear quantum-statistical effects, e.g., quantum tunneling and quantization of vibration. To systematically incorporate the quantum-statistical effects during MD simulations, we have developed an automated integration-free path-integral (AIF-PI) method based on Kleinert's variational perturbation theory for the centroid density of Feynman's path integral. Using this analytic method, we have performed ab initio pathintegral calculations to study the origin of KIEs on several series of proton-transfer reactions from carboxylic acids to aryl substituted alpha-methoxystyrenes in water. In addition, we also demonstrate that the AIF-PI method can be used to systematically compute the exact value of zero-point energy (beyond the harmonic approximation) by simply minimizing the centroid effective potential.

A kinetics database and scripts for PHREEQC

NASA Astrophysics Data System (ADS)

Hu, B.; Zhang, Y.; Teng, Y.; Zhu, C.

2017-12-01

Kinetics of geochemical reactions has been increasingly used in numerical models to simulate coupled flow, mass transport, and chemical reactions. However, the kinetic data are scattered in the literature. To assemble a kinetic dataset for a modeling project is an intimidating task for most. In order to facilitate the application of kinetics in geochemical modeling, we assembled kinetics parameters into a database for the geochemical simulation program, PHREEQC (version 3.0). Kinetics data were collected from the literature. Our database includes kinetic data for over 70 minerals. The rate equations are also programmed into scripts with the Basic language. Using the new kinetic database, we simulated reaction path during the albite dissolution process using various rate equations in the literature. The simulation results with three different rate equations gave difference reaction paths at different time scale. Another application involves a coupled reactive transport model simulating the advancement of an acid plume in an acid mine drainage site associated with Bear Creek Uranium tailings pond. Geochemical reactions including calcite, gypsum, and illite were simulated with PHREEQC using the new kinetic database. The simulation results successfully demonstrated the utility of new kinetic database.

Surfactants-aided syntheses of different sizes and triangular shape of gold nanoparticles using trisodium citrate in environmentally friendly and photoinduced methods.

PubMed

Su, Yen Hsun; Lai, Wei Hao; Chang, Shih-Hui; Hon, Min Hsiung

2007-09-01

We prepared gold nanoparticles (Au NPs) by only using trisodium citrate as the stabilizer. The detailed reaction mechanisms of S(N)1 and E1 reactions are examined and evidenced in this study by FTIR data. Citric acid is a kind of tertiary substrate. In aqueous solution, the substitution nucleophile path 1 (S(N)1) reaction and Elimination path 1 (E1) reaction usually occur simultaneously. Chloride ions, the substitution nucleophile, play a very important role to launch the mechanisms of S(N)1 and E1 reactions. Controlling the concentration of the chloride ions with the addition of HCl(aq) according to Le Chatelier theory, the average particle size of Au NPs (5.5 nm) was achieved to overcome the minimum limited size (approximately 10 nm). Two stages of the photoinduced method, aggregation into triangular conglomerates and growth into triangular particles, were determined form TEM observations. This preparation of Au NPs has potential in tuning the size, shape, and mechanism of Au NP formation by using only environmentally friendly trisodium citrate and the photoinduced method.

A FMO-controlled reaction path in the benzil-benzilic acid rearrangement.

PubMed

Yamabe, Shinichi; Tsuchida, Noriko; Yamazaki, Shoko

2006-03-03

Reaction paths for the title rearrangement along with its methyl analogue were investigated by density functional theory calculations. The reaction model is R-CO-CO-R + OH(-)(H2O)4 --> R2C(OH)-COO- + (H2O)4 (R = Me and Ph), where the water tetramer is employed both for solvation to OH- and for the proton relay along hydrogen bonds. The reaction is composed of OH- addition, C-C rotation, carbanion [1,2] migration, and proton relay toward the product anions. The rate-determining step was calculated to be the carbanion migration. Apparently, carbanion [1,2] migration is unlikely relative to the carbonium ion one. However, LUMOs of the 1,2-diketones have large and nodeless lobes at the reaction center, the C1-C2 bond. The specific LUMO character is reflected both in the [2+1]-like one-center nucleophilic addition and in the carbanion [1,2] shift. The proton relay involved in the isomerization from the oxo intermediate to the carboxylate was calculated to take place via the water tetramer.

Non-catalytic recuperative reformer

DOEpatents

Khinkis, Mark J.; Kozlov, Aleksandr P.; Kurek, Harry

2015-12-22

A non-catalytic recuperative reformer has a flue gas flow path for conducting hot flue gas from a thermal process and a reforming mixture flow path for conducting a reforming mixture. At least a portion of the reforming mixture flow path is embedded in the flue gas flow path to permit heat transfer from the hot flue gas to the reforming mixture. The reforming mixture flow path contains substantially no material commonly used as a catalyst for reforming hydrocarbon fuel (e.g., nickel oxide, platinum group elements or rhenium), but instead the reforming mixture is reformed into a higher calorific fuel via reactions due to the heat transfer and residence time. In a preferred embodiment, extended surfaces of metal material such as stainless steel or metal alloy that are high in nickel content are included within at least a portion of the reforming mixture flow path.

ELASTIC NET FOR COX'S PROPORTIONAL HAZARDS MODEL WITH A SOLUTION PATH ALGORITHM.

PubMed

Wu, Yichao

2012-01-01

For least squares regression, Efron et al. (2004) proposed an efficient solution path algorithm, the least angle regression (LAR). They showed that a slight modification of the LAR leads to the whole LASSO solution path. Both the LAR and LASSO solution paths are piecewise linear. Recently Wu (2011) extended the LAR to generalized linear models and the quasi-likelihood method. In this work we extend the LAR further to handle Cox's proportional hazards model. The goal is to develop a solution path algorithm for the elastic net penalty (Zou and Hastie (2005)) in Cox's proportional hazards model. This goal is achieved in two steps. First we extend the LAR to optimizing the log partial likelihood plus a fixed small ridge term. Then we define a path modification, which leads to the solution path of the elastic net regularized log partial likelihood. Our solution path is exact and piecewise determined by ordinary differential equation systems.

Optimisation des trajectoires d'un systeme de gestion de vol d'avions pour la reduction des couts de vol

NASA Astrophysics Data System (ADS)

Sidibe, Souleymane

The implementation and monitoring of operational flight plans is a major occupation for a crew of commercial flights. The purpose of this operation is to set the vertical and lateral trajectories followed by airplane during phases of flight: climb, cruise, descent, etc. These trajectories are subjected to conflicting economical constraints: minimization of flight time and minimization of fuel consumed and environmental constraints. In its task of mission planning, the crew is assisted by the Flight Management System (FMS) which is used to construct the path to follow and to predict the behaviour of the aircraft along the flight plan. The FMS considered in our research, particularly includes an optimization model of flight only by calculating the optimal speed profile that minimizes the overall cost of flight synthesized by a criterion of cost index following a steady cruising altitude. However, the model based solely on optimization of the speed profile is not sufficient. It is necessary to expand the current optimization for simultaneous optimization of the speed and altitude in order to determine an optimum cruise altitude that minimizes the overall cost when the path is flown with the optimal speed profile. Then, a new program was developed. The latter is based on the method of dynamic programming invented by Bellman to solve problems of optimal paths. In addition, the improvement passes through research new patterns of trajectories integrating ascendant cruises and using the lateral plane with the effect of the weather: wind and temperature. Finally, for better optimization, the program takes into account constraint of flight domain of aircrafts which utilize the FMS.

Species differences in unlocking B-side electron transfer in bacterial reaction centers

DOE PAGES

Dylla, Nicholas P.; Faries, Kaitlyn M.; Wyllie, Ryan M.; ...

2016-06-21

The structure of the bacterial photosynthetic reaction center (RC) reveals symmetry-related electron transfer (ET) pathways, but only one path is used in native RCs. Analogous mutations have been made in two Rhodobacter (R.) species. A glutamic acid at position 133 in the M subunit increases transmembrane charge separation via the naturally inactive (B-side) path through impacts on primary ET in mutant R. sphaeroidesRCs. Prior work showed that the analogous substitution in the R. capsulatusRC also increases B-side activity, but mainly affects secondary ET. Finally, the overall yields of transmembrane ET are similar, but enabled in fundamentally different ways.

Species differences in unlocking B-side electron transfer in bacterial reaction centers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dylla, Nicholas P.; Faries, Kaitlyn M.; Wyllie, Ryan M.

The structure of the bacterial photosynthetic reaction center (RC) reveals symmetry-related electron transfer (ET) pathways, but only one path is used in native RCs. Analogous mutations have been made in two Rhodobacter (R.) species. A glutamic acid at position 133 in the M subunit increases transmembrane charge separation via the naturally inactive (B-side) path through impacts on primary ET in mutant R. sphaeroidesRCs. Prior work showed that the analogous substitution in the R. capsulatusRC also increases B-side activity, but mainly affects secondary ET. Finally, the overall yields of transmembrane ET are similar, but enabled in fundamentally different ways.

Predictions of hydrothermal alteration within near-ridge oceanic crust from coordinated geochemical and fluid flow models

USGS Publications Warehouse

Wetzel, L.R.; Raffensperger, Jeff P.; Shock, E.L.

2001-01-01

Coordinated geochemical and hydrological calculations guide our understanding of the composition, fluid flow patterns, and thermal structure of near-ridge oceanic crust. The case study presented here illustrates geochemical and thermal changes taking place as oceanic crust ages from 0.2 to 1.0 Myr. Using a finite element code, we model fluid flow and heat transport through the upper few hundred meters of an abyssal hill created at an intermediate spreading rate. We use a reaction path model with a customized database to calculate equilibrium fluid compositions and mineral assemblages of basalt and seawater at 500 bars and temperatures ranging from 150 to 400??C. In one scenario, reaction path calculations suggest that volume increases on the order of 10% may occur within portions of the basaltic basement. If this change in volume occurred, it would be sufficient to fill all primary porosity in some locations, effectively sealing off portions of the oceanic crust. Thermal profiles resulting from fluid flow simulations indicate that volume changes along this possible reaction path occur primarily within the first 0.4 Myr of crustal aging. ?? 2001 Elsevier Science B.V. All rights reserved.

Reactive trajectories of the Ru2+/3+ self-exchange reaction and the connection to Marcus' theory.

PubMed

Tiwari, Ambuj; Ensing, Bernd

2016-12-22

Outer sphere electron transfer between two ions in aqueous solution is a rare event on the time scale of first principles molecular dynamics simulations. We have used transition path sampling to generate an ensemble of reactive trajectories of the self-exchange reaction between a pair of Ru 2+ and Ru 3+ ions in water. To distinguish between the reactant and product states, we use as an order parameter the position of the maximally localised Wannier center associated with the transferring electron. This allows us to align the trajectories with respect to the moment of barrier crossing and compute statistical averages over the path ensemble. We compare our order parameter with two typical reaction coordinates used in applications of Marcus theory of electron transfer: the vertical gap energy and the solvent electrostatic potential at the ions.

Design and Evaluation of a Dynamic Programming Flight Routing Algorithm Using the Convective Weather Avoidance Model

NASA Technical Reports Server (NTRS)

Ng, Hok K.; Grabbe, Shon; Mukherjee, Avijit

2010-01-01

The optimization of traffic flows in congested airspace with varying convective weather is a challenging problem. One approach is to generate shortest routes between origins and destinations while meeting airspace capacity constraint in the presence of uncertainties, such as weather and airspace demand. This study focuses on development of an optimal flight path search algorithm that optimizes national airspace system throughput and efficiency in the presence of uncertainties. The algorithm is based on dynamic programming and utilizes the predicted probability that an aircraft will deviate around convective weather. It is shown that the running time of the algorithm increases linearly with the total number of links between all stages. The optimal routes minimize a combination of fuel cost and expected cost of route deviation due to convective weather. They are considered as alternatives to the set of coded departure routes which are predefined by FAA to reroute pre-departure flights around weather or air traffic constraints. A formula, which calculates predicted probability of deviation from a given flight path, is also derived. The predicted probability of deviation is calculated for all path candidates. Routes with the best probability are selected as optimal. The predicted probability of deviation serves as a computable measure of reliability in pre-departure rerouting. The algorithm can also be extended to automatically adjust its design parameters to satisfy the desired level of reliability.

Children's Understanding of Psychogenic Bodily Reactions.

ERIC Educational Resources Information Center

Notaro, Paul C.; Gelman, Susan A.; Zimmerman, Marc A.

2001-01-01

Two studies compared how preschoolers through fifth graders and adults reasoned about psychogenic bodily reactions such as stress-induced headaches. Results supported a developmental path: younger children view psychogenic bodily responses as wholly physical, but with age, view them as both physical and psychological. (Author/KB)

Enzymatic Kinetic Isotope Effects from First-Principles Path Sampling Calculations.

PubMed

Varga, Matthew J; Schwartz, Steven D

2016-04-12

In this study, we develop and test a method to determine the rate of particle transfer and kinetic isotope effects in enzymatic reactions, specifically yeast alcohol dehydrogenase (YADH), from first-principles. Transition path sampling (TPS) and normal mode centroid dynamics (CMD) are used to simulate these enzymatic reactions without knowledge of their reaction coordinates and with the inclusion of quantum effects, such as zero-point energy and tunneling, on the transferring particle. Though previous studies have used TPS to calculate reaction rate constants in various model and real systems, it has not been applied to a system as large as YADH. The calculated primary H/D kinetic isotope effect agrees with previously reported experimental results, within experimental error. The kinetic isotope effects calculated with this method correspond to the kinetic isotope effect of the transfer event itself. The results reported here show that the kinetic isotope effects calculated from first-principles, purely for barrier passage, can be used to predict experimental kinetic isotope effects in enzymatic systems.

Evolvable Neuronal Paths: A Novel Basis for Information and Search in the Brain

PubMed Central

Fernando, Chrisantha; Vasas, Vera; Szathmáry, Eörs; Husbands, Phil

2011-01-01

We propose a previously unrecognized kind of informational entity in the brain that is capable of acting as the basis for unlimited hereditary variation in neuronal networks. This unit is a path of activity through a network of neurons, analogous to a path taken through a hidden Markov model. To prove in principle the capabilities of this new kind of informational substrate, we show how a population of paths can be used as the hereditary material for a neuronally implemented genetic algorithm, (the swiss-army knife of black-box optimization techniques) which we have proposed elsewhere could operate at somatic timescales in the brain. We compare this to the same genetic algorithm that uses a standard ‘genetic’ informational substrate, i.e. non-overlapping discrete genotypes, on a range of optimization problems. A path evolution algorithm (PEA) is defined as any algorithm that implements natural selection of paths in a network substrate. A PEA is a previously unrecognized type of natural selection that is well suited for implementation by biological neuronal networks with structural plasticity. The important similarities and differences between a standard genetic algorithm and a PEA are considered. Whilst most experiments are conducted on an abstract network model, at the conclusion of the paper a slightly more realistic neuronal implementation of a PEA is outlined based on Izhikevich spiking neurons. Finally, experimental predictions are made for the identification of such informational paths in the brain. PMID:21887266

Sensory feedback in a bump attractor model of path integration.

PubMed

Poll, Daniel B; Nguyen, Khanh; Kilpatrick, Zachary P

2016-04-01

Mammalian spatial navigation systems utilize several different sensory information channels. This information is converted into a neural code that represents the animal's current position in space by engaging place cell, grid cell, and head direction cell networks. In particular, sensory landmark (allothetic) cues can be utilized in concert with an animal's knowledge of its own velocity (idiothetic) cues to generate a more accurate representation of position than path integration provides on its own (Battaglia et al. The Journal of Neuroscience 24(19):4541-4550 (2004)). We develop a computational model that merges path integration with feedback from external sensory cues that provide a reliable representation of spatial position along an annular track. Starting with a continuous bump attractor model, we explore the impact of synaptic spatial asymmetry and heterogeneity, which disrupt the position code of the path integration process. We use asymptotic analysis to reduce the bump attractor model to a single scalar equation whose potential represents the impact of asymmetry and heterogeneity. Such imperfections cause errors to build up when the network performs path integration, but these errors can be corrected by an external control signal representing the effects of sensory cues. We demonstrate that there is an optimal strength and decay rate of the control signal when cues appear either periodically or randomly. A similar analysis is performed when errors in path integration arise from dynamic noise fluctuations. Again, there is an optimal strength and decay of discrete control that minimizes the path integration error.

Reactions and reaction rates in the regional aquifer beneath the Pajarito Plateau, north-central New Mexico, USA

NASA Astrophysics Data System (ADS)

Hereford, Anne G.; Keating, Elizabeth H.; Guthrie, George D.; Zhu, Chen

2007-05-01

Reactions and reaction rates within aquifers are fundamental components of critical hydrological processes. However, reactions simulated in laboratory experiments typically demonstrate rates that are much faster than those observed in the field. Therefore, it is necessary to conduct more reaction rate analyses in natural settings. This study of geochemical reactions in the regional aquifer in the Pajarito Plateau near Los Alamos, New Mexico combines modeling with petrographic assessment to further knowledge and understanding of complex natural hydrologic systems. Groundwater geochemistry shows marked evolution along assumed flow paths. The flow path chosen for this study was evaluated using inverse mass balance modeling to calculate the mass transfer. X-ray diffraction and field emission gun scanning electron microscopy were used to identify possible reactants and products. Considering the mineralogy of the aquifer and saturation indices for the regional water refined initial interpretations. Calculations yielded dissolution rates for plagioclase on the order of 10-15 mol s-1 m-2 and for K-feldspar on the order of 10-17 mol s-1 m-2, orders of magnitude slower than laboratory rates. While these rates agree with other aquifer studies, they must be considered in the light of the uncertainty associated with geometric surface area estimates, 14C ages, and aquifer properties.

Explanation of the unusual temperature dependence of the atmospherically important OH + H(2)S --> H(2)O + HS reaction and prediction of the rate constant at combustion temperatures.

PubMed

Ellingson, Benjamin A; Truhlar, Donald G

2007-10-24

Rate constants for the OH + H2S --> H2O + HS reaction, which is important for both atmospheric chemistry and combustion, are calculated by direct dynamics with the M06-2X density functional using the MG3S basis set. Energetics are compared to high-level MCG3/3//MC-QCISD/3 wave function theory and to results obtained by other density functionals. We employ canonical variational transition-state theory with multidimensional tunneling contributions and scaled generalized normal-mode frequencies evaluated in redundant curvilinear coordinates with anharmonicity included in the torsion. The transition state has a quantum mechanically distinguishable, nonsuperimposable mirror image that corresponds to a separate classical reaction path; the effect of the multiple paths is examined through use of a symmetry number and by torsional methods. Calculations with the reference-potential Pitzer-Gwinn treatment of the torsional mode agree with experiment, within experimental scatter, and predict a striking temperature dependence of the activation energy, increasing from -0.1 kcal/mol at 200 K to 0.2, 1.0, 3.4, and 9.8 kcal/mol at 300, 500, 1000, and 2400 K. The unusual temperature dependence arises from a dynamical bottleneck at an energy below reactants, following an addition complex on the reaction path with a classical binding energy of 4.4 kcal/mol. As a way to check the mechanism, kinetic isotope effects of the OH + D2S and OD + D2S reactions have been predicted.

MurD ligase from E. coli: Tetrahedral intermediate formation study by hybrid quantum mechanical/molecular mechanical replica path method.

PubMed

Perdih, Andrej; Hodoscek, Milan; Solmajer, Tom

2009-02-15

MurD (UDP-N-acetylmuramoyl-L-alanine:D-glutamate ligase), a three-domain bacterial protein, catalyses a highly specific incorporation of D-glutamate to the cytoplasmic intermediate UDP-N-acetyl-muramoyl-L-alanine (UMA) utilizing ATP hydrolysis to ADP and P(i). This reaction is part of a biosynthetic path yielding bacterial peptidoglycan. On the basis of structural studies of MurD complexes, a stepwise catalytic mechanism was proposed that commences with a formation of the acyl-phosphate intermediate, followed by a nucleophilic attack of D-glutamate that, through the formation of a tetrahedral reaction intermediate and subsequent phosphate dissociation, affords the final product, UDP-N-acetyl-muramoyl-L-alanine-D-glutamate (UMAG). A hybrid quantum mechanical/molecular mechanical (QM/MM) molecular modeling approach was utilized, combining the B3LYP QM level of theory with empirical force field simulations to evaluate three possible reaction pathways leading to tetrahedral intermediate formation. Geometries of the starting structures based on crystallographic experimental data and tetrahedral intermediates were carefully examined together with a role of crucial amino acids and water molecules. The replica path method was used to generate the reaction pathways between the starting structures and the corresponding tetrahedral reaction intermediates, offering direct comparisons with a sequential kinetic mechanism and the available structural data for this enzyme. The acquired knowledge represents new and valuable information to assist in the ongoing efforts leading toward novel inhibitors of MurD as potential antibacterial drugs. (c) 2008 Wiley-Liss, Inc.

Memory-efficient dynamic programming backtrace and pairwise local sequence alignment.

PubMed

Newberg, Lee A

2008-08-15

A backtrace through a dynamic programming algorithm's intermediate results in search of an optimal path, or to sample paths according to an implied probability distribution, or as the second stage of a forward-backward algorithm, is a task of fundamental importance in computational biology. When there is insufficient space to store all intermediate results in high-speed memory (e.g. cache) existing approaches store selected stages of the computation, and recompute missing values from these checkpoints on an as-needed basis. Here we present an optimal checkpointing strategy, and demonstrate its utility with pairwise local sequence alignment of sequences of length 10,000. Sample C++-code for optimal backtrace is available in the Supplementary Materials. Supplementary data is available at Bioinformatics online.

Path Planning For A Class Of Cutting Operations

NASA Astrophysics Data System (ADS)

Tavora, Jose

1989-03-01

Optimizing processing time in some contour-cutting operations requires solving the so-called no-load path problem. This problem is formulated and an approximate resolution method (based on heuristic search techniques) is described. Results for real-life instances (clothing layouts in the apparel industry) are presented and evaluated.

Understanding chemical binding using the Berlin function and the reaction force

NASA Astrophysics Data System (ADS)

Chakraborty, Debajit; Cárdenas, Carlos; Echegaray, Eleonora; Toro-Labbe, Alejandro; Ayers, Paul W.

2012-06-01

We use the derivative of the electron density with respect to the reaction coordinate, interpreted through the Berlin binding function, to identify portions of the reaction path where chemical bonds are breaking and forming. The results agree with the conventional description for SN2 reactions, but they are much more general and can be used to elucidate other types of reactions also. Our analysis offers support for, and detailed information about, the use of the reaction force profile to separate the reaction coordinates into intervals, each with characteristic extents of geometry change and electronic rearrangement.

Safe Maritime Autonomous Path Planning in a High Sea State

NASA Technical Reports Server (NTRS)

Ono, Masahiro; Quadrelli, Marco; Huntsberger, Terrance L.

2014-01-01

This paper presents a path planning method for sea surface vehicles that prevents capsizing and bow-diving in a high sea-state. A key idea is to use response amplitude operators (RAOs) or, in control terminology, the transfer functions from a sea state to a vessel's motion, in order to find a set of speeds and headings that results in excessive pitch and roll oscillations. This information is translated to arithmetic constraints on the ship's velocity, which are passed to a model predictive control (MPC)-based path planner to find a safe and optimal path that achieves specified goals. An obstacle avoidance capability is also added to the path planner. The proposed method is demonstrated by simulations.

Trajectory Generation and Path Planning for Autonomous Aerobots

NASA Technical Reports Server (NTRS)

Sharma, Shivanjli; Kulczycki, Eric A.; Elfes, Alberto

2007-01-01

This paper presents global path planning algorithms for the Titan aerobot based on user defined waypoints in 2D and 3D space. The algorithms were implemented using information obtained through a planner user interface. The trajectory planning algorithms were designed to accurately represent the aerobot's characteristics, such as minimum turning radius. Additionally, trajectory planning techniques were implemented to allow for surveying of a planar area based solely on camera fields of view, airship altitude, and the location of the planar area's perimeter. The developed paths allow for planar navigation and three-dimensional path planning. These calculated trajectories are optimized to produce the shortest possible path while still remaining within realistic bounds of airship dynamics.

Visual environment recognition for robot path planning using template matched filters

NASA Astrophysics Data System (ADS)

Orozco-Rosas, Ulises; Picos, Kenia; Díaz-Ramírez, Víctor H.; Montiel, Oscar; Sepúlveda, Roberto

2017-08-01

A visual approach in environment recognition for robot navigation is proposed. This work includes a template matching filtering technique to detect obstacles and feasible paths using a single camera to sense a cluttered environment. In this problem statement, a robot can move from the start to the goal by choosing a single path between multiple possible ways. In order to generate an efficient and safe path for mobile robot navigation, the proposal employs a pseudo-bacterial potential field algorithm to derive optimal potential field functions using evolutionary computation. Simulation results are evaluated in synthetic and real scenes in terms of accuracy of environment recognition and efficiency of path planning computation.

Cu deposited on CeOx-modified TiO 2(110): Synergistic effects at the metal–oxide interface and the mechanism of the WGS reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Plata, Jose J.; Graciani, Jesús; Evans, Jaime

2016-06-06

Experimental techniques and DFT calculations have been combined to study and compare the effect of the metal–substrate interaction in Cu/TiO 2(110) and Cu/CeO x/TiO 2(110) catalysts for the water–gas shift (WGS) reaction. Experiments and theory show that CeOx nanoparticles affect the dispersion of copper on titania, and on the formed copper–ceria interface, there are synergistic effects which favor water dissociation and the WGS reaction. The minimum energy path for the WGS reaction on the new highly active catalytic system Cu/CeO x/TiO 2(110) has been predicted by theoretical calculations. Main steps such as adsorption–dissociation of water and *OCOH carboxyl intermediate formation–deprotonationmore » have been characterized. In this very particular system, water splitting is no longer the rate-limiting step because it can dissociate overcoming an energy barrier of only 0.92 kcal/mol. One important insight of the present work is to show that easy full hydration of the ceria particles strongly lowers the reaction barrier for the deprotonation of the *OCOH intermediate and facilitates the evolution of the WGS reaction. For the first time, a system has been found on which the WGS reaction is able to work with all the involved energy barriers below 12 kcal/mol. This remarkable behavior makes the metal/CeO x/TiO 2 family a potential candidate for industrial application as catalysts in the WGS reaction. In conclusion, the change in the metal–support interactions when going from Cu/TiO 2 to Cu/CeO x/TiO 2 illustrates the importance of optimizing the oxide phase when improving the performance of metal/oxide catalysts for the WGS.« less

Kinetics and Thermodynamics of the Reaction between the (•)OH Radical and Adenine: A Theoretical Investigation.

PubMed

Milhøj, Birgitte O; Sauer, Stephan P A

2015-06-18

The accessibility of all possible reaction paths for the reaction between the nucleobase adenine and the (•)OH radical is investigated through quantum chemical calculations of barrier heights and rate constants at the ωB97X-D/6-311++G(2df,2pd) level with Eckart tunneling corrections. First the computational method is validated by considering the hydrogen abstraction from the heterocyclic N9 nitrogen in adenine as a test system. Geometries for all molecules in the reaction are optimized with four different DFT exchange-correlation functionals (B3LYP, BHandHLYP, M06-2X, and ωB97X-D), in combination with Pople and Dunning basis sets, all of which have been employed in similar investigations in the literature. Improved energies are obtained through single point calculations with CCSD(T) and the same basis sets, and reaction rate constants are calculated for all methods both without tunneling corrections and with the Wigner, Bell, and Eckart corrections. In comparison to CCSD(T)//BHandHLYP/aug-cc-pVTZ reference results, the ωB97X-D/6-311++G(2df,2pd) method combined with Eckart tunneling corrections provides a sensible compromise between accuracy and time. Using this method, all subreactions of the reaction between adenine and the (•)OH radical are investigated. The total rate constants for hydrogen abstraction and addition for adenine are predicted with this method to be 1.06 × 10(-12) and 1.10 × 10(-12) cm(3) molecules(-1) s(-1), respectively. Abstractions of H61 and H62 contribute the most, while only addition to the C8 carbon is found to be of any significance, in contrast to previous claims that addition is the dominant reaction pathway. The overall rate constant for the complete reaction is found to be 2.17 × 10(-12) cm(3) molecules(-1) s(-1), which agrees exceptionally well with experimental results.

The terminal area automated path generation problem

NASA Technical Reports Server (NTRS)

Hsin, C.-C.

1977-01-01

The automated terminal area path generation problem in the advanced Air Traffic Control System (ATC), has been studied. Definitions, input, output and the interrelationships with other ATC functions have been discussed. Alternatives in modeling the problem have been identified. Problem formulations and solution techniques are presented. In particular, the solution of a minimum effort path stretching problem (path generation on a given schedule) has been carried out using the Newton-Raphson trajectory optimization method. Discussions are presented on the effect of different delivery time, aircraft entry position, initial guess on the boundary conditions, etc. Recommendations are made on real-world implementations.

Path Planning for Robot based on Chaotic Artificial Potential Field Method

NASA Astrophysics Data System (ADS)

Zhang, Cheng

2018-03-01

Robot path planning in unknown environments is one of the hot research topics in the field of robot control. Aiming at the shortcomings of traditional artificial potential field methods, we propose a new path planning for Robot based on chaotic artificial potential field method. The path planning adopts the potential function as the objective function and introduces the robot direction of movement as the control variables, which combines the improved artificial potential field method with chaotic optimization algorithm. Simulations have been carried out and the results demonstrate that the superior practicality and high efficiency of the proposed method.

Optimization of IBF parameters based on adaptive tool-path algorithm

NASA Astrophysics Data System (ADS)

Deng, Wen Hui; Chen, Xian Hua; Jin, Hui Liang; Zhong, Bo; Hou, Jin; Li, An Qi

2018-03-01

As a kind of Computer Controlled Optical Surfacing(CCOS) technology. Ion Beam Figuring(IBF) has obvious advantages in the control of surface accuracy, surface roughness and subsurface damage. The superiority and characteristics of IBF in optical component processing are analyzed from the point of view of removal mechanism. For getting more effective and automatic tool path with the information of dwell time, a novel algorithm is proposed in this thesis. Based on the removal functions made through our IBF equipment and the adaptive tool-path, optimized parameters are obtained through analysis the residual error that would be created in the polishing process. A Φ600 mm plane reflector element was used to be a simulation instance. The simulation result shows that after four combinations of processing, the surface accuracy of PV (Peak Valley) value and the RMS (Root Mean Square) value was reduced to 4.81 nm and 0.495 nm from 110.22 nm and 13.998 nm respectively in the 98% aperture. The result shows that the algorithm and optimized parameters provide a good theoretical for high precision processing of IBF.

Analysis of explicit model predictive control for path-following control

PubMed Central

2018-01-01

In this paper, explicit Model Predictive Control(MPC) is employed for automated lane-keeping systems. MPC has been regarded as the key to handle such constrained systems. However, the massive computational complexity of MPC, which employs online optimization, has been a major drawback that limits the range of its target application to relatively small and/or slow problems. Explicit MPC can reduce this computational burden using a multi-parametric quadratic programming technique(mp-QP). The control objective is to derive an optimal front steering wheel angle at each sampling time so that autonomous vehicles travel along desired paths, including straight, circular, and clothoid parts, at high entry speeds. In terms of the design of the proposed controller, a method of choosing weighting matrices in an optimization problem and the range of horizons for path-following control are described through simulations. For the verification of the proposed controller, simulation results obtained using other control methods such as MPC, Linear-Quadratic Regulator(LQR), and driver model are employed, and CarSim, which reflects the features of a vehicle more realistically than MATLAB/Simulink, is used for reliable demonstration. PMID:29534080

Analysis of explicit model predictive control for path-following control.

PubMed

Lee, Junho; Chang, Hyuk-Jun

2018-01-01

In this paper, explicit Model Predictive Control(MPC) is employed for automated lane-keeping systems. MPC has been regarded as the key to handle such constrained systems. However, the massive computational complexity of MPC, which employs online optimization, has been a major drawback that limits the range of its target application to relatively small and/or slow problems. Explicit MPC can reduce this computational burden using a multi-parametric quadratic programming technique(mp-QP). The control objective is to derive an optimal front steering wheel angle at each sampling time so that autonomous vehicles travel along desired paths, including straight, circular, and clothoid parts, at high entry speeds. In terms of the design of the proposed controller, a method of choosing weighting matrices in an optimization problem and the range of horizons for path-following control are described through simulations. For the verification of the proposed controller, simulation results obtained using other control methods such as MPC, Linear-Quadratic Regulator(LQR), and driver model are employed, and CarSim, which reflects the features of a vehicle more realistically than MATLAB/Simulink, is used for reliable demonstration.

Serial robot for the trajectory optimization and error compensation of TMT mask exchange system

NASA Astrophysics Data System (ADS)

Wang, Jianping; Zhang, Feifan; Zhou, Zengxiang; Zhai, Chao

2015-10-01

Mask exchange system is the main part of Multi-Object Broadband Imaging Echellette (MOBIE) on the Thirty Meter Telescope (TMT). According to the conception of the TMT mask exchange system, the pre-design was introduced in the paper which was based on IRB 140 robot. The stiffness model of IRB 140 in SolidWorks was analyzed under different gravity vectors for further error compensation. In order to find the right location and path planning, the robot and the mask cassette model was imported into MOBIE model to perform different schemes simulation. And obtained the initial installation position and routing. Based on these initial parameters, IRB 140 robot was operated to simulate the path and estimate the mask exchange time. Meanwhile, MATLAB and ADAMS software were used to perform simulation analysis and optimize the route to acquire the kinematics parameters and compare with the experiment results. After simulation and experimental research mentioned in the paper, the theoretical reference was acquired which could high efficient improve the structure of the mask exchange system parameters optimization of the path and precision of the robot position.

Aircraft Trajectory Optimization and Contrails Avoidance in the Presence of Winds

NASA Technical Reports Server (NTRS)

Ng, Hok K.; Chen, Neil Y.

2010-01-01

There are indications that persistent contrails can lead to adverse climate change, although the complete effect on climate forcing is still uncertain. A flight trajectory optimization algorithm with fuel and contrails models, which develops alternative flight paths, provides policy makers the necessary data to make tradeoffs between persistent contrails mitigation and aircraft fuel consumption. This study develops an algorithm that calculates wind-optimal trajectories for cruising aircraft while avoiding the regions of airspace prone to persistent contrails formation. The optimal trajectories are developed by solving a non-linear optimal control problem with path constraints. The regions of airspace favorable to persistent contrails formation are modeled as penalty areas that aircraft should avoid and are adjustable. The tradeoff between persistent contrails formation and additional fuel consumption is investigated, with and without altitude optimization, for 12 city-pairs in the continental United States. Without altitude optimization, the reduction in contrail travel times is gradual with increase in total fuel consumption. When altitude is optimized, a two percent increase in total fuel consumption can reduce the total travel times through contrail regions by more than six times. Allowing further increase in fuel consumption does not seem to result in proportionate decrease in contrail travel times.

An improved artificial bee colony algorithm based on balance-evolution strategy for unmanned combat aerial vehicle path planning.

PubMed

Li, Bai; Gong, Li-gang; Yang, Wen-lun

2014-01-01

Unmanned combat aerial vehicles (UCAVs) have been of great interest to military organizations throughout the world due to their outstanding capabilities to operate in dangerous or hazardous environments. UCAV path planning aims to obtain an optimal flight route with the threats and constraints in the combat field well considered. In this work, a novel artificial bee colony (ABC) algorithm improved by a balance-evolution strategy (BES) is applied in this optimization scheme. In this new algorithm, convergence information during the iteration is fully utilized to manipulate the exploration/exploitation accuracy and to pursue a balance between local exploitation and global exploration capabilities. Simulation results confirm that BE-ABC algorithm is more competent for the UCAV path planning scheme than the conventional ABC algorithm and two other state-of-the-art modified ABC algorithms.

Optimizing concentration of shifter additive for plastic scintillators of different size

NASA Astrophysics Data System (ADS)

Adadurov, A. F.; Zhmurin, P. N.; Lebedev, V. N.; Titskaya, V. D.

2009-02-01

This paper concerns the influence of wavelength shifting (secondary) luminescent additive (LA 2) on the light yield of polystyrene-based plastic scintillator (PS) taking self-absorption into account. Calculations of light yield dependence on concentration of 1.4-bis(2-(5-phenyloxazolyl)-benzene (POPOP) as LA 2 were made for various path lengths of photons in PS. It is shown that there is an optimal POPOP concentration ( Copt), which provides a maximum light yield for a given path length. This optimal concentration is determined by the competition of luminescence and self-reflection processes. Copt values were calculated for PS of different dimensions. For small PS, Copt≈0.02%, which agree with a common (standard) value of POPOP concentration. For higher PS dimensions, the optimal POPOP concentration is decreased (to Copt≈0.006% for 320×30×2 cm sample), reducing the light yield from PS by almost 35%.

AC signal characterization for optimization of a CMOS single-electron pump

NASA Astrophysics Data System (ADS)

Murray, Roy; Perron, Justin K.; Stewart, M. D., Jr.; Zimmerman, Neil M.

2018-02-01

Pumping single electrons at a set rate is being widely pursued as an electrical current standard. Semiconductor charge pumps have been pursued in a variety of modes, including single gate ratchet, a variety of 2-gate ratchet pumps, and 2-gate turnstiles. Whether pumping with one or two AC signals, lower error rates can result from better knowledge of the properties of the AC signal at the device. In this work, we operated a CMOS single-electron pump with a 2-gate ratchet style measurement and used the results to characterize and optimize our two AC signals. Fitting this data at various frequencies revealed both a difference in signal path length and attenuation between our two AC lines. Using this data, we corrected for the difference in signal path length and attenuation by applying an offset in both the phase and the amplitude at the signal generator. Operating the device as a turnstile while using the optimized parameters determined from the 2-gate ratchet measurement led to much flatter, more robust charge pumping plateaus. This method was useful in tuning our device up for optimal charge pumping, and may prove useful to the semiconductor quantum dot community to determine signal attenuation and path differences at the device.

Optimal control to modelling motorcycle rider steering: local versus global coordinate systems in rider preview

NASA Astrophysics Data System (ADS)

Rowell, S.; Popov, A. A.; Meijaard, J. P.

2010-04-01

The response of a motorcycle is heavily dependent on the rider's control actions, and consequently a means of replicating the rider's behaviour provides an important extension to motorcycle dynamics. The primary objective here is to develop effective path-following simulations and to understand how riders control motorcycles. Optimal control theory is applied to the tracking of roadway by a motorcycle, using a non-linear motorcycle model operating in free control by steering torque input. A path-following controller with road preview is designed by minimising tracking errors and control effort. Tight controls with high weightings on performance and loose controls with high weightings on control power are defined. Special attention is paid to the modelling of multipoint preview in local and global coordinate systems. The controller model is simulated over a standard single lane-change manoeuvre. It is argued that the local coordinates point of view is more representative of the way that a human rider operates and interprets information. The simulations suggest that for accurate path following, using optimal control, the problem must be solved by the local coordinates approach in order to achieve accurate results with short preview horizons. Furthermore, some weaknesses of the optimal control approach are highlighted here.

Minimum Action Path Theory Reveals the Details of Stochastic Transitions Out of Oscillatory States

NASA Astrophysics Data System (ADS)

de la Cruz, Roberto; Perez-Carrasco, Ruben; Guerrero, Pilar; Alarcon, Tomas; Page, Karen M.

2018-03-01

Cell state determination is the outcome of intrinsically stochastic biochemical reactions. Transitions between such states are studied as noise-driven escape problems in the chemical species space. Escape can occur via multiple possible multidimensional paths, with probabilities depending nonlocally on the noise. Here we characterize the escape from an oscillatory biochemical state by minimizing the Freidlin-Wentzell action, deriving from it the stochastic spiral exit path from the limit cycle. We also use the minimized action to infer the escape time probability density function.

Total Solar Eclipse: “Through The Eyes of NASA,” Part 4

NASA Image and Video Library

2017-08-21

During the eclipse, 14 states across the U.S. were in the path of totality and experienced more than two minutes of darkness in the middle of the day – with a partial eclipse viewable all across North America. The broadcast – Eclipse Across America: Through the Eyes of NASA – covered locations along the path of totality, from Oregon to South Carolina including public reactions from all ages. The eclipse’s long path over land provided a unique opportunity to study the Sun, Earth, Moon and their interaction.

Total Solar Eclipse: “Through The Eyes of NASA,” Part 3

NASA Image and Video Library

2017-08-21

During the eclipse, 14 states across the U.S. were in the path of totality and experienced more than two minutes of darkness in the middle of the day – with a partial eclipse viewable all across North America. The broadcast – Eclipse Across America: Through the Eyes of NASA – covered locations along the path of totality, from Oregon to South Carolina including public reactions from all ages. The eclipse’s long path over land provided a unique opportunity to study the Sun, Earth, Moon and their interaction.

Minimum Action Path Theory Reveals the Details of Stochastic Transitions Out of Oscillatory States.

PubMed

de la Cruz, Roberto; Perez-Carrasco, Ruben; Guerrero, Pilar; Alarcon, Tomas; Page, Karen M

2018-03-23

Cell state determination is the outcome of intrinsically stochastic biochemical reactions. Transitions between such states are studied as noise-driven escape problems in the chemical species space. Escape can occur via multiple possible multidimensional paths, with probabilities depending nonlocally on the noise. Here we characterize the escape from an oscillatory biochemical state by minimizing the Freidlin-Wentzell action, deriving from it the stochastic spiral exit path from the limit cycle. We also use the minimized action to infer the escape time probability density function.

Comparison of Path Length and Ranges of Movement of the Center of Pressure and Reaction Time and Between Paired-Play and Solo-Play of a Virtual Reality Game.

PubMed

Portnoy, Sigal; Hersch, Ayelet; Sofer, Tal; Tresser, Sarit

2017-06-01

To test whether paired-play will induce longer path length and ranges of movement of the center of pressure (COP), which reflects on balance performance and stability, compared to solo-play and to test the difference in the path length and ranges of movement of the COP while playing the virtual reality (VR) game with the dominant hand compared to playing it with the nondominant hand. In this cross-sectional study 20 children (age 6.1 ± 0.7 years old) played an arm movement controlled VR game alone and with a peer while each of them stood on a pressure measuring pad to track the path length and ranges of movement of the COP. The total COP path was significantly higher during the paired-play (median 295.8 cm) compared to the COP path during the solo-play (median 189.2 cm). No significant differences were found in the reaction time and the mediolateral and anterior-posterior COP ranges between solo-play and paired-play. No significant differences were found between the parameters extracted during paired-play with the dominant or nondominant hand. Our findings imply that the paired-play is advantageous compared to solo-play since it induces a greater movement for the child, during which, higher COP velocities are reached that may contribute to improving the balance control of the child. Apart from the positive social benefits of paired-play, this positive effect on the COP path length is a noteworthy added value in the clinical setting when treating children with balance disorder.

Excitation of nucleobases from a computational perspective I: reaction paths.

PubMed

Giussani, Angelo; Segarra-Martí, Javier; Roca-Sanjuán, Daniel; Merchán, Manuela

2015-01-01

The main intrinsic photochemical events in nucleobases can be described on theoretical grounds within the realm of non-adiabatic computational photochemistry. From a static standpoint, the photochemical reaction path approach (PRPA), through the computation of the respective minimum energy path (MEP), can be regarded as the most suitable strategy in order to explore the electronically excited isolated nucleobases. Unfortunately, the PRPA does not appear widely in the studies reported in the last decade. The main ultrafast decay observed experimentally for the gas-phase excited nucleobases is related to the computed barrierless MEPs from the bright excited state connecting the initial Franck-Condon region and a conical intersection involving the ground state. At the highest level of theory currently available (CASPT2//CASPT2), the lowest excited (1)(ππ*) hypersurface for cytosine has a shallow minimum along the MEP deactivation pathway. In any case, the internal conversion processes in all the natural nucleobases are attained by means of interstate crossings, a self-protection mechanism that prevents the occurrence of photoinduced damage of nucleobases by ultraviolet radiation. Many alternative and secondary paths have been proposed in the literature, which ultimately provide a rich and constructive interplay between experimentally and theoretically oriented research.

Quasi-Monte Carlo Methods Applied to Tau-Leaping in Stochastic Biological Systems.

PubMed

Beentjes, Casper H L; Baker, Ruth E

2018-05-25

Quasi-Monte Carlo methods have proven to be effective extensions of traditional Monte Carlo methods in, amongst others, problems of quadrature and the sample path simulation of stochastic differential equations. By replacing the random number input stream in a simulation procedure by a low-discrepancy number input stream, variance reductions of several orders have been observed in financial applications. Analysis of stochastic effects in well-mixed chemical reaction networks often relies on sample path simulation using Monte Carlo methods, even though these methods suffer from typical slow [Formula: see text] convergence rates as a function of the number of sample paths N. This paper investigates the combination of (randomised) quasi-Monte Carlo methods with an efficient sample path simulation procedure, namely [Formula: see text]-leaping. We show that this combination is often more effective than traditional Monte Carlo simulation in terms of the decay of statistical errors. The observed convergence rate behaviour is, however, non-trivial due to the discrete nature of the models of chemical reactions. We explain how this affects the performance of quasi-Monte Carlo methods by looking at a test problem in standard quadrature.

Mechanisms and dynamics of protonation and lithiation of ferrocene.

PubMed

Sharma, Nishant; Ajay, Jayanth K; Venkatasubbaiah, Krishnan; Lourderaj, Upakarasamy

2015-09-14

By elucidating the mechanism of the simplest electrophilic substitution reaction of ferrocene, it was found that the verification of the protonation reaction has been a difficulty. In the work reported here, ab initio chemical dynamics simulations were performed at B3LYP/DZVP level of theory to understand the atomic level mechanisms of protonation and lithiation of ferrocene. Protonation of ferrocene resulted in the agostic and metal-protonated forms. Trajectory calculations revealed that protonation of ferrocene occurs by exo and endo mechanisms, with exo being the major path. H(+) was found to be mobile and hopped from the Cp ring to the metal center and vice versa after the initial attack on ferrocene, with the metal-complex having a shorter lifetime. These results remove the ambiguity surrounding the mechanism, as proposed in earlier experimental and computational studies. Lithiation of ferrocene resulted in the formation of cation-π and metal-lithiated complexes. Similar to protonation, trajectory results revealed that both exo and endo paths were followed, with the exo path being the major one. In addition, lithiated-ferrocene exhibited planetary motion. The major path (exo) followed in the protonation and lithiation of ferrocene is consistent with the observations in earlier experimental studies for other hard electrophiles.

Interactive multi-objective path planning through a palette-based user interface

NASA Astrophysics Data System (ADS)

Shaikh, Meher T.; Goodrich, Michael A.; Yi, Daqing; Hoehne, Joseph

2016-05-01

n a problem where a human uses supervisory control to manage robot path-planning, there are times when human does the path planning, and if satisfied commits those paths to be executed by the robot, and the robot executes that plan. In planning a path, the robot often uses an optimization algorithm that maximizes or minimizes an objective. When a human is assigned the task of path planning for robot, the human may care about multiple objectives. This work proposes a graphical user interface (GUI) designed for interactive robot path-planning when an operator may prefer one objective over others or care about how multiple objectives are traded off. The GUI represents multiple objectives using the metaphor of an artist's palette. A distinct color is used to represent each objective, and tradeoffs among objectives are balanced in a manner that an artist mixes colors to get the desired shade of color. Thus, human intent is analogous to the artist's shade of color. We call the GUI an "Adverb Palette" where the word "Adverb" represents a specific type of objective for the path, such as the adverbs "quickly" and "safely" in the commands: "travel the path quickly", "make the journey safely". The novel interactive interface provides the user an opportunity to evaluate various alternatives (that tradeoff between different objectives) by allowing her to visualize the instantaneous outcomes that result from her actions on the interface. In addition to assisting analysis of various solutions given by an optimization algorithm, the palette has additional feature of allowing the user to define and visualize her own paths, by means of waypoints (guiding locations) thereby spanning variety for planning. The goal of the Adverb Palette is thus to provide a way for the user and robot to find an acceptable solution even though they use very different representations of the problem. Subjective evaluations suggest that even non-experts in robotics can carry out the planning tasks with a great deal of flexibility using the adverb palette.

Microfluidics: a groundbreaking technology for PET tracer production?

PubMed

Rensch, Christian; Jackson, Alexander; Lindner, Simon; Salvamoser, Ruben; Samper, Victor; Riese, Stefan; Bartenstein, Peter; Wängler, Carmen; Wängler, Björn

2013-07-05

Application of microfluidics to Positron Emission Tomography (PET) tracer synthesis has attracted increasing interest within the last decade. The technical advantages of microfluidics, in particular the high surface to volume ratio and resulting fast thermal heating and cooling rates of reagents can lead to reduced reaction times, increased synthesis yields and reduced by-products. In addition automated reaction optimization, reduced consumption of expensive reagents and a path towards a reduced system footprint have been successfully demonstrated. The processing of radioactivity levels required for routine production, use of microfluidic-produced PET tracer doses in preclinical and clinical imaging as well as feasibility studies on autoradiolytic decomposition have all given promising results. However, the number of microfluidic synthesizers utilized for commercial routine production of PET tracers is very limited. This study reviews the state of the art in microfluidic PET tracer synthesis, highlighting critical design aspects, strengths, weaknesses and presenting several characteristics of the diverse PET market space which are thought to have a significant impact on research, development and engineering of microfluidic devices in this field. Furthermore, the topics of batch- and single-dose production, cyclotron to quality control integration as well as centralized versus de-centralized market distribution models are addressed.

A comparison of optimal and noise-abatement trajectories of a tilt-rotor aircraft

NASA Technical Reports Server (NTRS)

Schmitz, F. H.; Stepniewski, W. Z.; Gibs, J.; Hinterkeuser, W. Z.

1972-01-01

The potential benefits of flight path control to optimize performance and/or reduce the noise of a tilt-rotor aircraft operating in the takeoff and landing phases of flight are investigated. A theoretical performance-acoustic model is developed and then mathematically flown to yield representative takeoff and landing profiles. Minimum-time and minimum-fuel trajectories are compared to proposed noise-abatement profiles to assess the reductions in annoyance possible through flight path control. Significant reductions are feasible if a nearly vertical-takeoff flight profile is flown near the landing site; however, the time expended and fuel consumed increase.

Protein Folding Free Energy Landscape along the Committor - the Optimal Folding Coordinate.

PubMed

Krivov, Sergei V

2018-06-06

Recent advances in simulation and experiment have led to dramatic increases in the quantity and complexity of produced data, which makes the development of automated analysis tools very important. A powerful approach to analyze dynamics contained in such data sets is to describe/approximate it by diffusion on a free energy landscape - free energy as a function of reaction coordinates (RC). For the description to be quantitatively accurate, RCs should be chosen in an optimal way. Recent theoretical results show that such an optimal RC exists; however, determining it for practical systems is a very difficult unsolved problem. Here we describe a solution to this problem. We describe an adaptive nonparametric approach to accurately determine the optimal RC (the committor) for an equilibrium trajectory of a realistic system. In contrast to alternative approaches, which require a functional form with many parameters to approximate an RC and thus extensive expertise with the system, the suggested approach is nonparametric and can approximate any RC with high accuracy without system specific information. To avoid overfitting for a realistically sampled system, the approach performs RC optimization in an adaptive manner by focusing optimization on less optimized spatiotemporal regions of the RC. The power of the approach is illustrated on a long equilibrium atomistic folding simulation of HP35 protein. We have determined the optimal folding RC - the committor, which was confirmed by passing a stringent committor validation test. It allowed us to determine a first quantitatively accurate protein folding free energy landscape. We have confirmed the recent theoretical results that diffusion on such a free energy profile can be used to compute exactly the equilibrium flux, the mean first passage times, and the mean transition path times between any two points on the profile. We have shown that the mean squared displacement along the optimal RC grows linear with time as for simple diffusion. The free energy profile allowed us to obtain a direct rigorous estimate of the pre-exponential factor for the folding dynamics.

Electrode assembly for use in a solid polymer electrolyte fuel cell

DOEpatents

Raistrick, Ian D.

1989-01-01

A gas reaction fuel cell may be provided with a solid polymer electrolyte membrane. Porous gas diffusion electrodes are formed of carbon particles supporting a catalyst which is effective to enhance the gas reactions. The carbon particles define interstitial spaces exposing the catalyst on a large surface area of the carbon particles. A proton conducting material, such as a perfluorocarbon copolymer or ruthenium dioxide contacts the surface areas of the carbon particles adjacent the interstitial spaces. The proton conducting material enables protons produced by the gas reactions adjacent the supported catalyst to have a conductive path with the electrolyte membrane. The carbon particles provide a conductive path for electrons. A suitable electrode may be formed by dispersing a solution containing a proton conducting material over the surface of the electrode in a manner effective to coat carbon surfaces adjacent the interstitial spaces without impeding gas flow into the interstitial spaces.

Implications of path tolerance and path characteristics on critical vehicle manoeuvres

NASA Astrophysics Data System (ADS)

Lundahl, K.; Frisk, E.; Nielsen, L.

2017-12-01

Path planning and path following are core components in safe autonomous driving. Typically, a path planner provides a path with some tolerance on how tightly the path should be followed. Based on that, and other path characteristics, for example, sharpness of curves, a speed profile needs to be assigned so that the vehicle can stay within the given tolerance without going unnecessarily slow. Here, such trajectory planning is based on optimal control formulations where critical cases arise as on-the-limit solutions. The study focuses on heavy commercial vehicles, causing rollover to be of a major concern, due to the relatively high centre of gravity. Several results are obtained on required model complexity depending on path characteristics, for example, quantification of required path tolerance for a simple model to be sufficient, quantification of when yaw inertia needs to be considered in more detail, and how the curvature rate of change interplays with available friction. Overall, in situations where the vehicle is subject to a wide range of driving conditions, from good transport roads to more tricky avoidance manoeuvres, the requirements on the path following will vary. For this, the provided results form a basis for real-time path following.

An estimate of the shadow price of water in the southern Ogallala Aquifer

USDA-ARS?s Scientific Manuscript database

In this paper, we attempt to quantify the shadow price of an additional inch of groundwater resource left in situ for the Southern Ogallala Aquifer. Previous authors have shown the degree to which the optimal resource extraction path may diverge from the competitive extraction path based upon varyin...

Terrain Following Control Based on an Optimized Spline Model of Aircraft Motion

DTIC Science & Technology

1975-11-01

constraints, a smooth path through the final data points may not satisfy the norma acceleration constraints between sample points. This latter assertion is...for the reference path in the table. Sae copromise betwen the two effects is required. The accelerations given in Table 7-2 are those measured at the

Redox reaction rates in shallow aquifers: Implications for nitrate transport in groundwater and streams

USGS Publications Warehouse

Tesoriero, Anthony J.

2012-01-01

Groundwater age and water chemistry data along flow paths from recharge areas to streams were used to evaluate the trends and transformations of agricultural chemicals. Results from this analysis indicate that median nitrate recharge concentrations in these agricultural areas have increased markedly over the last 50 years from 4 mg N/L in samples collected prior to 1983 to 7.5 mg N/L in samples collected since 1983. The effect that nitrate accumulation in shallow aquifers will have on drinking water quality and stream ecosystems is dependent on the rate of redox reactions along flow paths and on the age distribution of nitrate discharging to supply wells and streams.

Catalytic hydrodeoxygenation of methyl-substituted phenols: correlations of kinetic parameters with molecular properties.

PubMed

Massoth, F E; Politzer, P; Concha, M C; Murray, J S; Jakowski, J; Simons, Jack

2006-07-27

The hydrodeoxygenation of methyl-substituted phenols was carried out in a flow microreactor at 300 degrees C and 2.85 MPa hydrogen pressure over a sulfided CoMo/Al(2)O(3) catalyst. The primary reaction products were methyl-substituted benzene, cyclohexene, cyclohexane, and H(2)O. Analysis of the results suggests that two independent reaction paths are operative, one leading to aromatics and the other to partially or completely hydrogenated cyclohexanes. The reaction data were analyzed using Langmuir-Hinshelwood kinetics to extract the values of the reactant-to-catalyst adsorption constant and of the rate constants characterizing the two reaction paths. The adsorption constant was found to be the same for both reactions, suggesting that a single catalytic site center is operative in both reactions. Ab initio electronic structure calculations were used to evaluate the electrostatic potentials and valence orbital ionization potentials for all of the substituted phenol reactants. Correlations were observed between (a) the adsorption constant and the two reaction rate constants measured for various methyl-substitutions and (b) certain moments of the electrostatic potentials and certain orbitals' ionization potentials of the isolated phenol molecules. On the basis of these correlations to intrinsic reactant-molecule properties, a reaction mechanism is proposed for each pathway, and it is suggested that the dependencies of adsorption and reaction rates upon methyl-group substitution are a result of the substituents' effects on the electrostatic potential and orbitals rather than geometric (steric) effects.

Computation of rare transitions in the barotropic quasi-geostrophic equations

NASA Astrophysics Data System (ADS)

Laurie, Jason; Bouchet, Freddy

2015-01-01

We investigate the theoretical and numerical computation of rare transitions in simple geophysical turbulent models. We consider the barotropic quasi-geostrophic and two-dimensional Navier-Stokes equations in regimes where bistability between two coexisting large-scale attractors exist. By means of large deviations and instanton theory with the use of an Onsager-Machlup path integral formalism for the transition probability, we show how one can directly compute the most probable transition path between two coexisting attractors analytically in an equilibrium (Langevin) framework and numerically otherwise. We adapt a class of numerical optimization algorithms known as minimum action methods to simple geophysical turbulent models. We show that by numerically minimizing an appropriate action functional in a large deviation limit, one can predict the most likely transition path for a rare transition between two states. By considering examples where theoretical predictions can be made, we show that the minimum action method successfully predicts the most likely transition path. Finally, we discuss the application and extension of such numerical optimization schemes to the computation of rare transitions observed in direct numerical simulations and experiments and to other, more complex, turbulent systems.

jFuzz: A Concolic Whitebox Fuzzer for Java

NASA Technical Reports Server (NTRS)

Jayaraman, Karthick; Harvison, David; Ganesh, Vijay; Kiezun, Adam

2009-01-01

We present jFuzz, a automatic testing tool for Java programs. jFuzz is a concolic whitebox fuzzer, built on the NASA Java PathFinder, an explicit-state Java model checker, and a framework for developing reliability and analysis tools for Java. Starting from a seed input, jFuzz automatically and systematically generates inputs that exercise new program paths. jFuzz uses a combination of concrete and symbolic execution, and constraint solving. Time spent on solving constraints can be significant. We implemented several well-known optimizations and name-independent caching, which aggressively normalizes the constraints to reduce the number of calls to the constraint solver. We present preliminary results due to the optimizations, and demonstrate the effectiveness of jFuzz in creating good test inputs. The source code of jFuzz is available as part of the NASA Java PathFinder. jFuzz is intended to be a research testbed for investigating new testing and analysis techniques based on concrete and symbolic execution. The source code of jFuzz is available as part of the NASA Java PathFinder.

Unraveling the Processing Parameters in Friction Stir Welding

NASA Technical Reports Server (NTRS)

Schneider, Judy; Nunes, Arthur C., Jr.

2005-01-01

In friction stir welding (FSW), a rotating threaded pin tool is translated along a weld seam, literally stirring the edges of the seam together. To determine optimal processing parameters for producing a defect free weld, a better understanding of the resulting metal deformation flow path or paths is required. In this study, various markers are used to trace the flow paths of the metal. X-ray radiographs record the segmentation and position of the wire. Several variations in the trajectories can be differentiated within the weld zone.

Cooperative 3D Path Optimization (C3PO) Simulation

DTIC Science & Technology

2015-11-10

is the starting point for the path. As branches are added, they are checked to make sure they meet the requirements that the unmanned vehicle (UV...tune the maximum branch size for the tree to get longer branches. It makes sense that in open space this would lead to smaller (by number of nodes...starting with very high maximum branch size and gradually make it smaller as suitable paths can’t be found. The authors would also like to try this

Anger and health in dementia caregivers: exploring the mediation effect of optimism.

PubMed

López, J; Romero-Moreno, R; Márquez-González, M; Losada, A

2015-04-01

Although previous studies indicate a negative association between caregivers' anger and health, the potential mechanisms linking this relationship are not yet fully understood. The aim of this study was to explore the potential mediating role of optimism in the relationship between anger and caregivers' physical health. Dementia caregivers (n = 108) were interviewed and filled out instruments assessing their anger (reaction), optimism and health (vitality). A mediational model was tested to determine whether optimism partially mediated the relationship between anger and vitality. Angry reaction was negatively associated with optimism and vitality; optimism was positively associated with vitality. Finally, the relationship between angry reaction and vitality decreased when optimism was entered simultaneously. A non-parametric bootstrap approach confirmed that optimism significantly mediated some of the relationship between angry reaction and vitality. These findings suggest that low optimism may help explain the association between caregivers' anger and reduced sense of vitality. The results provide a specific target for intervention with caregivers. Copyright © 2013 John Wiley & Sons, Ltd.

Transitioning NWChem to the Next Generation of Manycore Machines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bylaska, Eric J.; Apra, Edoardo; Kowalski, Karol

The NorthWest Chemistry (NWChem) modeling software is a popular molecular chemistry simulation software that was designed from the start to work on massively parallel processing supercomputers[6, 28, 49]. It contains an umbrella of modules that today includes Self Consistent Field (SCF), second order Mller-Plesset perturbation theory (MP2), Coupled Cluster, multi-conguration selfconsistent eld (MCSCF), selected conguration interaction (CI), tensor contraction engine (TCE) many body methods, density functional theory (DFT), time-dependent density functional theory (TDDFT), real time time-dependent density functional theory, pseudopotential plane-wave density functional theory (PSPW), band structure (BAND), ab initio molecular dynamics, Car-Parrinello molecular dynamics, classical molecular dynamics (MD), QM/MM,more » AIMD/MM, GIAO NMR, COSMO, COSMO-SMD, and RISM solvation models, free energy simulations, reaction path optimization, parallel in time, among other capabilities[ 22]. Moreover new capabilities continue to be added with each new release.« less

Utilization of High-Temperature Slags From Metallurgy Based on Crystallization Behaviors

NASA Astrophysics Data System (ADS)

Sun, Yongqi; Zhang, Zuotai

2018-05-01

Here, following the principle of modifying crystallization behaviors, including avoidance and optimization, we review recent research on the utilization of hot slags. Because of the high-temperature property (1450-1650°C), the utilization of hot slags are much different from that of other wastes. We approach this issue from two main directions, namely, material recycling and heat utilization. From the respect of material recycling, the utilization of slags mainly follows total utilization and partial utilization, whereas the heat recovery from slags follows two main paths, namely, physical granulation and chemical reaction. The effective disposal of hot slags greatly depends on clarifying the crystallization behaviors, and thus, we discuss some optical techniques and their applicable scientific insights. For the purpose of crystallization avoidance, characterizing the glass-forming ability of slags is of great significance, whereas for crystallization modification, the selection of chemical additives and control of crystallization conditions comprise the central routes.

Bifurcations on Potential Energy Surfaces of Organic Reactions

PubMed Central

Ess, Daniel H.; Wheeler, Steven E.; Iafe, Robert G.; Xu, Lai; Çelebi-Ölçüm, Nihan; Houk, K. N.

2009-01-01

A single transition state may lead to multiple intermediates or products if there is a post-transition state reaction path bifurcation. These bifurcations arise when there are sequential transition states with no intervening energy minimum. For such systems, the shape of the potential energy surface and dynamic effects control selectivity rather than transition state energetics. This minireview covers recent investigations of organic reactions exhibiting reaction pathway bifurcations. Such phenomena are surprisingly general and affect experimental observables such as kinetic isotope effects and product distributions. PMID:18767086

Optimal path planning for video-guided smart munitions via multitarget tracking

NASA Astrophysics Data System (ADS)

Borkowski, Jeffrey M.; Vasquez, Juan R.

2006-05-01

An advent in the development of smart munitions entails autonomously modifying target selection during flight in order to maximize the value of the target being destroyed. A unique guidance law can be constructed that exploits both attribute and kinematic data obtained from an onboard video sensor. An optimal path planning algorithm has been developed with the goals of obstacle avoidance and maximizing the value of the target impacted by the munition. Target identification and classification provides a basis for target value which is used in conjunction with multi-target tracks to determine an optimal waypoint for the munition. A dynamically feasible trajectory is computed to provide constraints on the waypoint selection. Results demonstrate the ability of the autonomous system to avoid moving obstacles and revise target selection in flight.

ELASTIC NET FOR COX’S PROPORTIONAL HAZARDS MODEL WITH A SOLUTION PATH ALGORITHM

PubMed Central

Wu, Yichao

2012-01-01

For least squares regression, Efron et al. (2004) proposed an efficient solution path algorithm, the least angle regression (LAR). They showed that a slight modification of the LAR leads to the whole LASSO solution path. Both the LAR and LASSO solution paths are piecewise linear. Recently Wu (2011) extended the LAR to generalized linear models and the quasi-likelihood method. In this work we extend the LAR further to handle Cox’s proportional hazards model. The goal is to develop a solution path algorithm for the elastic net penalty (Zou and Hastie (2005)) in Cox’s proportional hazards model. This goal is achieved in two steps. First we extend the LAR to optimizing the log partial likelihood plus a fixed small ridge term. Then we define a path modification, which leads to the solution path of the elastic net regularized log partial likelihood. Our solution path is exact and piecewise determined by ordinary differential equation systems. PMID:23226932

Production of Solar-Grade Silicon by the SiF4 and Mg Reaction

NASA Astrophysics Data System (ADS)

Xie, Xiaobing; Bao, Jianer; Sanjurjo, Angel

2016-12-01

Over 90 pct of the solar cells currently produced and installed are Si based, and this industrial dominance is expected to persist for the foreseeable future. The crystalline Si substrate accounts for a significant portion of the total cost of solar cells. In order to further reduce the cost of solar panels, there has been significant effort in producing inexpensive solar-grade Si, mainly through three paths: (1) modification of the Siemens process to lower production costs, (2) upgrading metallurgical-grade Si to reach solar-grade purity, and (3) by means of new metallurgical processes such as the reduction of a silicon halide, e.g., SiF4 or SiCl4, by a reactive metal such as Na or Zn. In this paper, we describe an alternative path that uses Mg to react with SiF4 to produce low-cost solar grade Si. Experimental conditions for complete reaction and separation of the products, Si and MgF2, as well as aspects of the reaction mechanism are described. The reaction involves both a heterogeneous liquid-gas phase reaction and a homogeneous gas-gas phase reaction. When pure Mg was used, the Si product obtained had sub-ppm levels of B and P impurities and is expected to be suitable for solar cell applications.

Development and validation of chemistry agnostic flow battery cost performance model and application to nonaqueous electrolyte systems: Chemistry agnostic flow battery cost performance model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crawford, Alasdair; Thomsen, Edwin; Reed, David

2016-04-20

A chemistry agnostic cost performance model is described for a nonaqueous flow battery. The model predicts flow battery performance by estimating the active reaction zone thickness at each electrode as a function of current density, state of charge, and flow rate using measured data for electrode kinetics, electrolyte conductivity, and electrode-specific surface area. Validation of the model is conducted using a 4kW stack data at various current densities and flow rates. This model is used to estimate the performance of a nonaqueous flow battery with electrode and electrolyte properties used from the literature. The optimized cost for this system ismore » estimated for various power and energy levels using component costs provided by vendors. The model allows optimization of design parameters such as electrode thickness, area, flow path design, and operating parameters such as power density, flow rate, and operating SOC range for various application duty cycles. A parametric analysis is done to identify components and electrode/electrolyte properties with the highest impact on system cost for various application durations. A pathway to 100$kWh -1 for the storage system is identified.« less

Unraveling the role of water in the stereoselective step of aqueous proline-catalyzed aldol reactions.

PubMed

Ribas-Arino, Jordi; Carvajal, Maria Angels; Chaumont, Alain; Masia, Marco

2012-12-03

A multiscale computational study was performed with the aim of tracing the source of stereoselectivity and disclosing the role of water in the stereoselective step of propionaldehyde aldol self-condensation catalyzed by proline amide in water, a reaction that serves as a model for aqueous organocatalytic aldol condensations. Solvent mixing and hydration behavior were assessed by classical molecular dynamics simulations, which show that the reaction between propanal and the corresponding enamine takes place in a fully hydrated environment. First-principles molecular dynamics simulations were used to study the free-energy profile of four possible reaction paths, each of which yields a different stereoisomer, and high-level static first-principles calculations were employed to characterize the transition states for microsolvated species. The first solvation shell of the oxygen atom of the electrophilic aldehyde at the transition states contains two water molecules, each of which donates one hydrogen bond to the nascent alkoxide and thereby largely stabilizes its excess electron density. The stereoselectivity originates in an extra hydrogen bond donated by the amido group of proline amide in two reaction paths. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inverse optimal self-tuning PID control design for an autonomous underwater vehicle

NASA Astrophysics Data System (ADS)

Rout, Raja; Subudhi, Bidyadhar

2017-01-01

This paper presents a new approach to path following control design for an autonomous underwater vehicle (AUV). A NARMAX model of the AUV is derived first and then its parameters are adapted online using the recursive extended least square algorithm. An adaptive Propotional-Integral-Derivative (PID) controller is developed using the derived parameters to accomplish the path following task of an AUV. The gain parameters of the PID controller are tuned using an inverse optimal control technique, which alleviates the problem of solving Hamilton-Jacobian equation and also satisfies an error cost function. Simulation studies were pursued to verify the efficacy of the proposed control algorithm. From the obtained results, it is envisaged that the proposed NARMAX model-based self-tuning adaptive PID control provides good path following performance even in the presence of uncertainty arising due to ocean current or hydrodynamic parameter.

Multiagent Flight Control in Dynamic Environments with Cooperative Coevolutionary Algorithms

NASA Technical Reports Server (NTRS)

Knudson, Matthew D.; Colby, Mitchell; Tumer, Kagan

2014-01-01

Dynamic flight environments in which objectives and environmental features change with respect to time pose a difficult problem with regards to planning optimal flight paths. Path planning methods are typically computationally expensive, and are often difficult to implement in real time if system objectives are changed. This computational problem is compounded when multiple agents are present in the system, as the state and action space grows exponentially. In this work, we use cooperative coevolutionary algorithms in order to develop policies which control agent motion in a dynamic multiagent unmanned aerial system environment such that goals and perceptions change, while ensuring safety constraints are not violated. Rather than replanning new paths when the environment changes, we develop a policy which can map the new environmental features to a trajectory for the agent while ensuring safe and reliable operation, while providing 92% of the theoretically optimal performance

Multiagent Flight Control in Dynamic Environments with Cooperative Coevolutionary Algorithms

NASA Technical Reports Server (NTRS)

Colby, Mitchell; Knudson, Matthew D.; Tumer, Kagan

2014-01-01

Dynamic environments in which objectives and environmental features change with respect to time pose a difficult problem with regards to planning optimal paths through these environments. Path planning methods are typically computationally expensive, and are often difficult to implement in real time if system objectives are changed. This computational problem is compounded when multiple agents are present in the system, as the state and action space grows exponentially with the number of agents in the system. In this work, we use cooperative coevolutionary algorithms in order to develop policies which control agent motion in a dynamic multiagent unmanned aerial system environment such that goals and perceptions change, while ensuring safety constraints are not violated. Rather than replanning new paths when the environment changes, we develop a policy which can map the new environmental features to a trajectory for the agent while ensuring safe and reliable operation, while providing 92% of the theoretically optimal performance.

Genetic Algorithm for Traveling Salesman Problem with Modified Cycle Crossover Operator

PubMed Central

Mohamd Shoukry, Alaa; Gani, Showkat

2017-01-01

Genetic algorithms are evolutionary techniques used for optimization purposes according to survival of the fittest idea. These methods do not ensure optimal solutions; however, they give good approximation usually in time. The genetic algorithms are useful for NP-hard problems, especially the traveling salesman problem. The genetic algorithm depends on selection criteria, crossover, and mutation operators. To tackle the traveling salesman problem using genetic algorithms, there are various representations such as binary, path, adjacency, ordinal, and matrix representations. In this article, we propose a new crossover operator for traveling salesman problem to minimize the total distance. This approach has been linked with path representation, which is the most natural way to represent a legal tour. Computational results are also reported with some traditional path representation methods like partially mapped and order crossovers along with new cycle crossover operator for some benchmark TSPLIB instances and found improvements. PMID:29209364

Genetic Algorithm for Traveling Salesman Problem with Modified Cycle Crossover Operator.

PubMed

Hussain, Abid; Muhammad, Yousaf Shad; Nauman Sajid, M; Hussain, Ijaz; Mohamd Shoukry, Alaa; Gani, Showkat

2017-01-01

Genetic algorithms are evolutionary techniques used for optimization purposes according to survival of the fittest idea. These methods do not ensure optimal solutions; however, they give good approximation usually in time. The genetic algorithms are useful for NP-hard problems, especially the traveling salesman problem. The genetic algorithm depends on selection criteria, crossover, and mutation operators. To tackle the traveling salesman problem using genetic algorithms, there are various representations such as binary, path, adjacency, ordinal, and matrix representations. In this article, we propose a new crossover operator for traveling salesman problem to minimize the total distance. This approach has been linked with path representation, which is the most natural way to represent a legal tour. Computational results are also reported with some traditional path representation methods like partially mapped and order crossovers along with new cycle crossover operator for some benchmark TSPLIB instances and found improvements.

Optimization of pyrochlore catalysts for the dry reforming of methane

NASA Astrophysics Data System (ADS)

Polo Garzon, Felipe

The conversion of methane into syngas (a mixture of CO and H2), which can be further converted into a variety of chemicals and particularly liquid fuels, is of growing importance given recent increases in methane production world-wide. Furthermore, since using CO2 as the co-feed offers many environmental advantages, dry reforming of methane (DRM, CH4 + CO2 [special character omitted] 2CO + 2H 2) has received renewed attention. In recent years, experimentalists have shown that the Rh-substituted lanthanum zirconate pyrochlore (LRhZ) material is catalytically active for DRM, exhibits long-term thermal stability and resists deactivation; however, previous to this doctoral work, a detailed understanding of the reaction mechanism on pyrochlore catalyst surfaces was still scarce, making it difficult to optimize this material. In this work, initial computational efforts employing density functional theory (DFT) showed the plane (111) of the LRhZ crystal structure as the one catalytically active for DRM. In addition, the primary reaction pathway was identified, along with two rate determining steps (RDSs), the CH2 oxygenation step and the CHO dehydrogenation step, which lie on the CH 4 dehydrogenation/oxygenation path. The mechanistic understanding of DRM over LRhZ was further developed using steady-state isotopic transient kinetic analysis (SSITKA). Reversible adsorption of CO2 on the surface was observed, along with short surface residence times (< 0.6 s) at 650 and 800 °C, and increasing turnover frequencies with temperature. Comparisons between isotopic responses supported the DFT-derived reaction mechanism. Furthermore, isotopic transient kinetics confirmed that all metal atoms (Rh, Zr and La) on the surface are involved in the reaction mechanism, as previously pointed by DFT calculations. A DFT-based microkinetic model that predicts the reaction performance at different conditions was built. The model was validated against experimental data, showing remarkable agreement, which further confirmed the reliability of the DFT data. Computational analysis of one of the RDSs (the CHO dehydrogenation step) suggested Pd as an effective co-dopant to reduce the activation barrier of this step. This bimetallic Rh-Pd-substituted lanthanum zirconate pyrochlore (Rh-Pd-LZ) was synthesized, characterized and tested. The Rh-Pd-LZ catalyst successfully increased conversions at high temperatures while providing H 2 to CO ratios close to unity; thus fostering DRM and inhibiting the competing reaction, the reverse water gas shift reaction (RWGS, CO2 + H2 [special character omitted] CO + H2O). The Rh-Pd-LZ catalyst outperformed the initial catalyst, the LRhZ, at high temperatures.

Introduction of a computer-based method for automated planning of reduction paths under consideration of simulated muscular forces.

PubMed

Buschbaum, Jan; Fremd, Rainer; Pohlemann, Tim; Kristen, Alexander

2017-08-01

Reduction is a crucial step in the surgical treatment of bone fractures. Finding an optimal path for restoring anatomical alignment is considered technically demanding because collisions as well as high forces caused by surrounding soft tissues can avoid desired reduction movements. The repetition of reduction movements leads to a trial-and-error process which causes a prolonged duration of surgery. By planning an appropriate reduction path-an optimal sequence of target-directed movements-these problems should be overcome. For this purpose, a computer-based method has been developed. Using the example of simple femoral shaft fractures, 3D models are generated out of CT images. A reposition algorithm aligns both fragments by reconstructing their broken edges. According to the criteria of a deduced planning strategy, a modified A*-algorithm searches collision-free route of minimal force from the dislocated into the computed target position. Muscular forces are considered using a musculoskeletal reduction model (OpenSim model), and bone collisions are detected by an appropriate method. Five femoral SYNBONE models were broken into different fracture classification types and were automatically reduced from ten randomly selected displaced positions. Highest mean translational and rotational error for achieving target alignment is [Formula: see text] and [Formula: see text]. Mean value and standard deviation of occurring forces are [Formula: see text] for M. tensor fasciae latae and [Formula: see text] for M. semitendinosus over all trials. These pathways are precise, collision-free, required forces are minimized, and thus regarded as optimal paths. A novel method for planning reduction paths under consideration of collisions and muscular forces is introduced. The results deliver additional knowledge for an appropriate tactical reduction procedure and can provide a basis for further navigated or robotic-assisted developments.

Graph drawing using tabu search coupled with path relinking.

PubMed

Dib, Fadi K; Rodgers, Peter

2018-01-01

Graph drawing, or the automatic layout of graphs, is a challenging problem. There are several search based methods for graph drawing which are based on optimizing an objective function which is formed from a weighted sum of multiple criteria. In this paper, we propose a new neighbourhood search method which uses a tabu search coupled with path relinking to optimize such objective functions for general graph layouts with undirected straight lines. To our knowledge, before our work, neither of these methods have been previously used in general multi-criteria graph drawing. Tabu search uses a memory list to speed up searching by avoiding previously tested solutions, while the path relinking method generates new solutions by exploring paths that connect high quality solutions. We use path relinking periodically within the tabu search procedure to speed up the identification of good solutions. We have evaluated our new method against the commonly used neighbourhood search optimization techniques: hill climbing and simulated annealing. Our evaluation examines the quality of the graph layout (objective function's value) and the speed of layout in terms of the number of evaluated solutions required to draw a graph. We also examine the relative scalability of each method. Our experimental results were applied to both random graphs and a real-world dataset. We show that our method outperforms both hill climbing and simulated annealing by producing a better layout in a lower number of evaluated solutions. In addition, we demonstrate that our method has greater scalability as it can layout larger graphs than the state-of-the-art neighbourhood search methods. Finally, we show that similar results can be produced in a real world setting by testing our method against a standard public graph dataset.

Graph drawing using tabu search coupled with path relinking

PubMed Central

Rodgers, Peter

2018-01-01

Graph drawing, or the automatic layout of graphs, is a challenging problem. There are several search based methods for graph drawing which are based on optimizing an objective function which is formed from a weighted sum of multiple criteria. In this paper, we propose a new neighbourhood search method which uses a tabu search coupled with path relinking to optimize such objective functions for general graph layouts with undirected straight lines. To our knowledge, before our work, neither of these methods have been previously used in general multi-criteria graph drawing. Tabu search uses a memory list to speed up searching by avoiding previously tested solutions, while the path relinking method generates new solutions by exploring paths that connect high quality solutions. We use path relinking periodically within the tabu search procedure to speed up the identification of good solutions. We have evaluated our new method against the commonly used neighbourhood search optimization techniques: hill climbing and simulated annealing. Our evaluation examines the quality of the graph layout (objective function’s value) and the speed of layout in terms of the number of evaluated solutions required to draw a graph. We also examine the relative scalability of each method. Our experimental results were applied to both random graphs and a real-world dataset. We show that our method outperforms both hill climbing and simulated annealing by producing a better layout in a lower number of evaluated solutions. In addition, we demonstrate that our method has greater scalability as it can layout larger graphs than the state-of-the-art neighbourhood search methods. Finally, we show that similar results can be produced in a real world setting by testing our method against a standard public graph dataset. PMID:29746576

A new, double-inversion mechanism of the F- + CH3Cl SN2 reaction in aqueous solution.

PubMed

Liu, Peng; Wang, Dunyou; Xu, Yulong

2016-11-23

Atomic-level, bimolecular nucleophilic substitution reaction mechanisms have been studied mostly in the gas phase, but the gas-phase results cannot be expected to reliably describe condensed-phase chemistry. As a novel, double-inversion mechanism has just been found for the F - + CH 3 Cl S N 2 reaction in the gas phase [Nat. Commun., 2015, 6, 5972], here, using multi-level quantum mechanics methods combined with the molecular mechanics method, we discovered a new, double-inversion mechanism for this reaction in aqueous solution. However, the structures of the stationary points along the reaction path show significant differences from those in the gas phase due to the strong influence of solvent and solute interactions, especially due to the hydrogen bonds formed between the solute and the solvent. More importantly, the relationship between the two double-inversion transition states is not clear in the gas phase, but, here we revealed a novel intermediate complex serving as a "connecting link" between the two transition states of the abstraction-induced inversion and the Walden-inversion mechanisms. A detailed reaction path was constructed to show the atomic-level evolution of this novel double reaction mechanism in aqueous solution. The potentials of mean force were calculated and the obtained Walden-inversion barrier height agrees well with the available experimental value.

Constraining Path-Dependent Processes During Basalt-CO2 Interactions with Observations From Flow-Through and Batch Experiments

NASA Astrophysics Data System (ADS)

Thomas, D.; Garing, C.; Zahasky, C.; Harrison, A. L.; Bird, D. K.; Benson, S. M.; Oelkers, E. H.; Maher, K.

2017-12-01

Predicting the timing and magnitude of CO2 storage in basaltic rocks relies partly on quantifying the dependence of reactivity on flow path and mineral distribution. Flow-through experiments that use intact cores are advantageous because the spatial heterogeneity of pore space and reactive phases is preserved. Combining aqueous geochemical analyses and petrologic characterization with non-destructive imaging techniques (e.g. micro-computed tomography) constrains the relationship between irreversible reactions, pore connectivity and accessible surface area. Our work enhances these capabilities by dynamically imaging flow through vesicular basalts with Positron Emission Tomography (PET) scanning. PET highlights the path a fluid takes by detecting photons produced during radioactive decay of an injected radiotracer (FDG). We have performed single-phase, CO2-saturated flow-through experiments with basaltic core from Iceland at CO2 sequestration conditions (50 °C; 76-90 bar Ptot). Constant flow rate and continuous pressure measurements at the inlet and outlet of the core constrain permeability. We monitor geochemical evolution through cation and anion analysis of outlet fluid sampled periodically. Before and after reaction, we perform PET scans and characterize the core using micro-CT. The PET scans indicate a discrete, localized flow path that appears to be a micro-crack connecting vesicles, suggesting that vesicle-lining minerals are immediately accessible and important reactants. Rapid increases in aqueous cation concentration, pH and HCO3- indicate that the rock reacts nearly immediately after CO2 injection. After 24 hours the solute release decreases, which may reflect a transition to reaction with phases with slower kinetic dissolution rates (e.g. zeolites and glasses to feldspar), a decrease in available reactive surface area or precipitation. We have performed batch experiments using crushed material of the same rock to elucidate the effect of flow path geometry and mineral accessibility on geochemical evolution. Interestingly, surface area-normalized dissolution rates as evinced by SiO2 release in all experiments approach similar values ( 10-15 mol/cm2/s). Our experiments show how imaging techniques are helpful in interpreting path-dependent processes in open systems.

Theoretical Study of the Mechanism of Oxoiron(IV) Formation from H2O2 and a Nonheme Iron(II) Complex: O–O Cleavage Involving Proton-Coupled Electron Transfer

PubMed Central

Hirao, Hajime; Li, Feifei; Que, Lawrence; Morokuma, Keiji

2011-01-01

It has recently been shown that the nonheme oxoiron(IV) species supported by the 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane ligand (TMC) can be generated in near-quantitative yield by reacting [FeII(TMC)(OTf)2] with a stoichiometric amount of H2O2 in CH3CN in the presence of 2,6-lutidine (Li, F.; England, J.; Que L., Jr. J. Am. Chem. Soc. 2010, 132, 2134–2135). This finding has major implications for O–O bond cleavage events in both Fenton chemistry and nonheme iron enzymes. To understand the mechanism of this process, especially the intimate details of the O–O bond cleavage step, a series of density functional theory (DFT) calculations and analyses have been carried out. Two distinct reaction paths (A and B) were identified. Path A consists of two principal steps: (1) coordination of H2O2 to Fe(II) and (2) a combination of partial homolytic O–O bond cleavage and proton-coupled electron transfer (PCET). The latter combination renders the rate-limiting O–O cleavage effectively a heterolytic process. Path B proceeds via a simultaneous homolytic O–O bond cleavage of H2O2 and Fe–O bond formation. This is followed by H-abstraction from the resultant Fe(III)–OH species by an •OH radical. Calculations suggest that path B is plausible in the absence of base. However, once 2,6-lutidine is added to the reacting system, the reaction barrier is lowered and more importantly the mechanistic path switches to path A, where 2,6-lutidine plays an essential role as an acid-base catalyst in a manner similar to how the distal histidine or glutamate residue assists in Compound I formation in heme peroxidases. The reaction was found to proceed predominantly on the quintet spin state surface, and a transition to the triplet state, the experimentally known ground state for the TMC-oxoiron(IV) species, occurs in the last stage of the oxoiron(IV) formation process. PMID:21678930

Use of combined radar and radiometer systems in space for precipitation measurement: Some ideas

NASA Technical Reports Server (NTRS)

Moore, R. K.

1981-01-01

A brief survey is given of some fundamental physical concepts of optimal polarization characteristics of a transmission path or scatter ensemble of hydrometers. It is argued that, based on this optimization concept, definite advances in remote atmospheric sensing are to be expected. Basic properties of Kennaugh's optimal polarization theory are identified.

Improved Modeling of Intelligent Tutoring Systems Using Ant Colony Optimization

ERIC Educational Resources Information Center

Rastegarmoghadam, Mahin; Ziarati, Koorush

2017-01-01

Swarm intelligence approaches, such as ant colony optimization (ACO), are used in adaptive e-learning systems and provide an effective method for finding optimal learning paths based on self-organization. The aim of this paper is to develop an improved modeling of adaptive tutoring systems using ACO. In this model, the learning object is…

Design Genetic Algorithm Optimization Education Software Based Fuzzy Controller for a Tricopter Fly Path Planning

ERIC Educational Resources Information Center

Tran, Huu-Khoa; Chiou, Juing -Shian; Peng, Shou-Tao

2016-01-01

In this paper, the feasibility of a Genetic Algorithm Optimization (GAO) education software based Fuzzy Logic Controller (GAO-FLC) for simulating the flight motion control of Unmanned Aerial Vehicles (UAVs) is designed. The generated flight trajectories integrate the optimized Scaling Factors (SF) fuzzy controller gains by using GAO algorithm. The…

Do Dogs Know Related Rates Rather than Optimization?

ERIC Educational Resources Information Center

Perruchet, Pierre; Gallego, Jorge

2006-01-01

Although dogs seemingly follow the optimal path where they get to a ball thrown into the water, they certainly do not know the minimization function proposed in the calculus books. Trading the optimization problem for a related rates problem leads to a mathematically identical solution, which, it is argued here, is a more plausible model for the…

The dissociative chemisorption of methane on Ni(100) and Ni(111): Classical and quantum studies based on the reaction path Hamiltonian

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mastromatteo, Michael; Jackson, Bret, E-mail: jackson@chem.umass.edu

Electronic structure methods based on density functional theory are used to construct a reaction path Hamiltonian for CH{sub 4} dissociation on the Ni(100) and Ni(111) surfaces. Both quantum and quasi-classical trajectory approaches are used to compute dissociative sticking probabilities, including all molecular degrees of freedom and the effects of lattice motion. Both approaches show a large enhancement in sticking when the incident molecule is vibrationally excited, and both can reproduce the mode specificity observed in experiments. However, the quasi-classical calculations significantly overestimate the ground state dissociative sticking at all energies, and the magnitude of the enhancement in sticking with vibrationalmore » excitation is much smaller than that computed using the quantum approach or observed in the experiments. The origin of this behavior is an unphysical flow of zero point energy from the nine normal vibrational modes into the reaction coordinate, giving large values for reaction at energies below the activation energy. Perturbative assumptions made in the quantum studies are shown to be accurate at all energies studied.« less

N-nitrosodimethylamine (NDMA) as a product of potassium permanganate reaction with aqueous solutions of dimethylamine (DMA).

PubMed

Andrzejewski, Przemysław; Nawrocki, Jacek

2009-03-01

The reactivity of permanganate with dimethylamine, as possible path of NDMA formation, has been investigated. The results have shown that potassium permanganate reaction with aqueous solutions of dimethylamine (DMA) leads to the formation of N-nitrosodimethylamine (NDMA). The contact time, the molar ratio of permanganate and DMA, pH and presence of nitrite are the key factors influencing the efficiency of NDMA formation. Significant conversion rates of DMA to NDMA were observed only for the high doses of permanganate, which were many times higher than those typically used in water treatment. This reaction however is of importance for water treatment technology, since it shows the possibility of NDMA formation as a result of oxidation of DMA. It is likely that nitrosation is the main path of the reaction. An important role of MnO2 suspension, formed as a result of permanganate reduction in NDMA formation is emphasized. Significant influence of MnO2 suspension on NDMA formation should draw our attention to the potential impact of MnO2 activated filtration beds on NDMA formation.

The role of Fenton reaction in ROS-induced toxicity underlying atherosclerosis - modeled and analyzed using a Petri net-based approach.

PubMed

Formanowicz, Dorota; Radom, Marcin; Rybarczyk, Agnieszka; Formanowicz, Piotr

2018-03-01

The superoxide-driven Fenton reaction plays an important role in the transformation of poorly reactive radicals into highly reactive ones. These highly reactive species (ROS), especially hydroxyl radicals can lead to many disturbances contributing to the endothelial dysfunction being a starting point for atherosclerosis. Although, iron has been identified as a possible culprit influencing formation of ROS, its significance in this process is still debatable. To better understand this phenomenon, the influence of blockade of Fenton reaction in a proposed Petri net-based model of the selected aspects of the iron ROS-induced toxicity in atherosclerosis has been evaluated. As a result of the blockade of iron ions formation in the model, even up to 70% of the paths leading to the progression of atherosclerosis in this model has been blocked. In addition, after adding to the model, the blockade of the lipids peroxidation paths, progression of atherosclerotic plaque has been not observed. This allowed to conclude that the superoxide-driven Fenton reaction plays a significant role in the atherosclerosis. Copyright © 2018 Elsevier B.V. All rights reserved.

Rate Constant and Reaction Coordinate of Trp-Cage Folding in Explicit Water

PubMed Central

Juraszek, Jarek; Bolhuis, Peter G.

2008-01-01

We report rate constant calculations and a reaction coordinate analysis of the rate-limiting folding and unfolding process of the Trp-cage mini-protein in explicit solvent using transition interface sampling. Previous transition path sampling simulations revealed that in this (un)folding process the protein maintains its compact configuration, while a (de)increase of secondary structure is observed. The calculated folding rate agrees reasonably with experiment, while the unfolding rate is 10 times higher. We discuss possible origins for this mismatch. We recomputed the rates with the forward flux sampling method, and found a discrepancy of four orders of magnitude, probably caused by the method's higher sensitivity to the choice of order parameter with respect to transition interface sampling. Finally, we used the previously computed transition path-sampling ensemble to screen combinations of many order parameters for the best model of the reaction coordinate by employing likelihood maximization. We found that a combination of the root mean-square deviation of the helix and of the entire protein was, of the set of tried order parameters, the one that best describes the reaction coordination. PMID:18676648

Optimal multiguidance integration in insect navigation.

PubMed

Hoinville, Thierry; Wehner, Rüdiger

2018-03-13

In the last decades, desert ants have become model organisms for the study of insect navigation. In finding their way, they use two major navigational routines: path integration using a celestial compass and landmark guidance based on sets of panoramic views of the terrestrial environment. It has been claimed that this information would enable the insect to acquire and use a centralized cognitive map of its foraging terrain. Here, we present a decentralized architecture, in which the concurrently operating path integration and landmark guidance routines contribute optimally to the directions to be steered, with "optimal" meaning maximizing the certainty (reliability) of the combined information. At any one time during its journey, the animal computes a path integration (global) vector and landmark guidance (local) vector, in which the length of each vector is proportional to the certainty of the individual estimates. Hence, these vectors represent the limited knowledge that the navigator has at any one place about the direction of the goal. The sum of the global and local vectors indicates the navigator's optimal directional estimate. Wherever applied, this decentralized model architecture is sufficient to simulate the results of quite a number of diverse cue-conflict experiments, which have recently been performed in various behavioral contexts by different authors in both desert ants and honeybees. They include even those experiments that have deliberately been designed by former authors to strengthen the evidence for a metric cognitive map in bees.

Comparison of primary optics in amonix CPV arrays

NASA Astrophysics Data System (ADS)

Nayak, Aditya; Kinsey, Geoffrey S.; Liu, Mingguo; Bagienski, William; Garboushian, Vahan

2012-10-01

The Amonix CPV system utilizes an acrylic Fresnel lens Primary Optical Element (POE) and a reflective Secondary Optical Element (SOE). Improvements in the optical design have contributed to more than 10% increase in rated power last year. In order to further optimize the optical power path, Amonix is looking at various trade-offs in optics, including, concentration, optical materials, reliability, and cost. A comparison of optical materials used for manufacturing the primary optical element and optical design trade off's used to maximize power output will be presented. Optimization of the power path has led to the demonstration of a module lens-area efficiency of 35% in outdoor testing at Amonix.

Development of Advanced Methods of Structural and Trajectory Analysis for Transport Aircraft

NASA Technical Reports Server (NTRS)

Ardema, Mark D.; Windhorst, Robert; Phillips, James

1998-01-01

This paper develops a near-optimal guidance law for generating minimum fuel, time, or cost fixed-range trajectories for supersonic transport aircraft. The approach uses a choice of new state variables along with singular perturbation techniques to time-scale decouple the dynamic equations into multiple equations of single order (second order for the fast dynamics). Application of the maximum principle to each of the decoupled equations, as opposed to application to the original coupled equations, avoids the two point boundary value problem and transforms the problem from one of a functional optimization to one of multiple function optimizations. It is shown that such an approach produces well known aircraft performance results such as minimizing the Brequet factor for minimum fuel consumption and the energy climb path. Furthermore, the new state variables produce a consistent calculation of flight path angle along the trajectory, eliminating one of the deficiencies in the traditional energy state approximation. In addition, jumps in the energy climb path are smoothed out by integration of the original dynamic equations at constant load factor. Numerical results performed for a supersonic transport design show that a pushover dive followed by a pullout at nominal load factors are sufficient maneuvers to smooth the jump.

Algorithms for Heterogeneous, Multiple Depot, Multiple Unmanned Vehicle Path Planning Problems

DOE PAGES

Sundar, Kaarthik; Rathinam, Sivakumar

2016-12-26

Unmanned vehicles, both aerial and ground, are being used in several monitoring applications to collect data from a set of targets. This article addresses a problem where a group of heterogeneous aerial or ground vehicles with different motion constraints located at distinct depots visit a set of targets. The vehicles also may be equipped with different sensors, and therefore, a target may not be visited by any vehicle. The objective is to find an optimal path for each vehicle starting and ending at its respective depot such that each target is visited at least once by some vehicle, the vehicle–targetmore » constraints are satisfied, and the sum of the length of the paths for all the vehicles is minimized. Two variants of this problem are formulated (one for ground vehicles and another for aerial vehicles) as mixed-integer linear programs and a branchand- cut algorithm is developed to compute an optimal solution to each of the variants. Computational results show that optimal solutions for problems involving 100 targets and 5 vehicles can be obtained within 300 seconds on average, further corroborating the effectiveness of the proposed approach.« less

RetroPath2.0: A retrosynthesis workflow for metabolic engineers.

PubMed

Delépine, Baudoin; Duigou, Thomas; Carbonell, Pablo; Faulon, Jean-Loup

2018-01-01

Synthetic biology applied to industrial biotechnology is transforming the way we produce chemicals. However, despite advances in the scale and scope of metabolic engineering, the research and development process still remains costly. In order to expand the chemical repertoire for the production of next generation compounds, a major engineering biology effort is required in the development of novel design tools that target chemical diversity through rapid and predictable protocols. Addressing that goal involves retrosynthesis approaches that explore the chemical biosynthetic space. However, the complexity associated with the large combinatorial retrosynthesis design space has often been recognized as the main challenge hindering the approach. Here, we provide RetroPath2.0, an automated open source workflow for retrosynthesis based on generalized reaction rules that perform the retrosynthesis search from chassis to target through an efficient and well-controlled protocol. Its easiness of use and the versatility of its applications make this tool a valuable addition to the biological engineer bench desk. We show through several examples the application of the workflow to biotechnological relevant problems, including the identification of alternative biosynthetic routes through enzyme promiscuity or the development of biosensors. We demonstrate in that way the ability of the workflow to streamline retrosynthesis pathway design and its major role in reshaping the design, build, test and learn pipeline by driving the process toward the objective of optimizing bioproduction. The RetroPath2.0 workflow is built using tools developed by the bioinformatics and cheminformatics community, because it is open source we anticipate community contributions will likely expand further the features of the workflow. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

Alternative Constraint Handling Technique for Four-Bar Linkage Path Generation

NASA Astrophysics Data System (ADS)

Sleesongsom, S.; Bureerat, S.

2018-03-01

This paper proposes an extension of a new concept for path generation from our previous work by adding a new constraint handling technique. The propose technique was initially designed for problems without prescribed timing by avoiding the timing constraint, while remain constraints are solving with a new constraint handling technique. The technique is one kind of penalty technique. The comparative study is optimisation of path generation problems are solved using self-adaptive population size teaching-learning based optimization (SAP-TLBO) and original TLBO. In this study, two traditional path generation test problem are used to test the proposed technique. The results show that the new technique can be applied with the path generation problem without prescribed timing and gives better results than the previous technique. Furthermore, SAP-TLBO outperforms the original one.

The navigation system of the JPL robot

NASA Technical Reports Server (NTRS)

Thompson, A. M.

1977-01-01

The control structure of the JPL research robot and the operations of the navigation subsystem are discussed. The robot functions as a network of interacting concurrent processes distributed among several computers and coordinated by a central executive. The results of scene analysis are used to create a segmented terrain model in which surface regions are classified by traversibility. The model is used by a path planning algorithm, PATH, which uses tree search methods to find the optimal path to a goal. In PATH, the search space is defined dynamically as a consequence of node testing. Maze-solving and the use of an associative data base for context dependent node generation are also discussed. Execution of a planned path is accomplished by a feedback guidance process with automatic error recovery.

Ab initio study of C + H3+ reactions

NASA Technical Reports Server (NTRS)

Talbi, D.; DeFrees, D. J.

1991-01-01

The reaction C + H3+ --> CH(+) + H2 is frequently used in models of dense interstellar cloud chemistry with the assumption that it is fast, i.e. there are no potential energy barriers inhibiting it. Ab initio molecular orbital study of the triplet CH3+ potential energy surface (triplet because the reactant carbon atom is a ground state triplet) supports this hypothesis. The reaction product is 3 pi CH+; the reaction is to exothermic even though the product is not in its electronic ground state. No path has been found on the potential energy surface for C + H3+ --> CH2(+) + H reaction.

A Robot Trajectory Optimization Approach for Thermal Barrier Coatings Used for Free-Form Components

NASA Astrophysics Data System (ADS)

Cai, Zhenhua; Qi, Beichun; Tao, Chongyuan; Luo, Jie; Chen, Yuepeng; Xie, Changjun

2017-10-01

This paper is concerned with a robot trajectory optimization approach for thermal barrier coatings. As the requirements of high reproducibility of complex workpieces increase, an optimal thermal spraying trajectory should not only guarantee an accurate control of spray parameters defined by users (e.g., scanning speed, spray distance, scanning step, etc.) to achieve coating thickness homogeneity but also help to homogenize the heat transfer distribution on the coating surface. A mesh-based trajectory generation approach is introduced in this work to generate path curves on a free-form component. Then, two types of meander trajectories are generated by performing a different connection method. Additionally, this paper presents a research approach for introducing the heat transfer analysis into the trajectory planning process. Combining heat transfer analysis with trajectory planning overcomes the defects of traditional trajectory planning methods (e.g., local over-heating), which helps form the uniform temperature field by optimizing the time sequence of path curves. The influence of two different robot trajectories on the process of heat transfer is estimated by coupled FEM models which demonstrates the effectiveness of the presented optimization approach.

An Effective Hybrid Routing Algorithm in WSN: Ant Colony Optimization in combination with Hop Count Minimization.

PubMed

Jiang, Ailian; Zheng, Lihong

2018-03-29

Low cost, high reliability and easy maintenance are key criteria in the design of routing protocols for wireless sensor networks (WSNs). This paper investigates the existing ant colony optimization (ACO)-based WSN routing algorithms and the minimum hop count WSN routing algorithms by reviewing their strengths and weaknesses. We also consider the critical factors of WSNs, such as energy constraint of sensor nodes, network load balancing and dynamic network topology. Then we propose a hybrid routing algorithm that integrates ACO and a minimum hop count scheme. The proposed algorithm is able to find the optimal routing path with minimal total energy consumption and balanced energy consumption on each node. The algorithm has unique superiority in terms of searching for the optimal path, balancing the network load and the network topology maintenance. The WSN model and the proposed algorithm have been implemented using C++. Extensive simulation experimental results have shown that our algorithm outperforms several other WSN routing algorithms on such aspects that include the rate of convergence, the success rate in searching for global optimal solution, and the network lifetime.

An Effective Hybrid Routing Algorithm in WSN: Ant Colony Optimization in combination with Hop Count Minimization

PubMed Central

2018-01-01

Low cost, high reliability and easy maintenance are key criteria in the design of routing protocols for wireless sensor networks (WSNs). This paper investigates the existing ant colony optimization (ACO)-based WSN routing algorithms and the minimum hop count WSN routing algorithms by reviewing their strengths and weaknesses. We also consider the critical factors of WSNs, such as energy constraint of sensor nodes, network load balancing and dynamic network topology. Then we propose a hybrid routing algorithm that integrates ACO and a minimum hop count scheme. The proposed algorithm is able to find the optimal routing path with minimal total energy consumption and balanced energy consumption on each node. The algorithm has unique superiority in terms of searching for the optimal path, balancing the network load and the network topology maintenance. The WSN model and the proposed algorithm have been implemented using C++. Extensive simulation experimental results have shown that our algorithm outperforms several other WSN routing algorithms on such aspects that include the rate of convergence, the success rate in searching for global optimal solution, and the network lifetime. PMID:29596336

Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt3M (M=Pt, Ru, Sn, Re, Rh, and Pd)

PubMed Central

Xu, Zhen-Feng; Wang, Yixuan

2011-01-01

The adsorption and dehydrogenation reactions of ethanol over bimetallic clusters, Pt3M (M = Pt, Ru, Sn, Re, Rh, and Pd), have been extensively investigated with density functional theory. Both the α-hydrogen and hydroxyl adsorptions on Pt as well as on the alloyed transition metal M sites of PtM were considered as initial reaction steps. The adsorptions of ethanol on Pt and M sites of some PtM via the α-hydrogen were well established. Although the α-hydrogen adsorption on Pt site is weaker than the hydroxyl, the potential energy profiles show that the dehydrogenation via the α-hydrogen path has much lower energy barrier than that via the hydroxyl path. Generally for the α-hydrogen path the adsorption is a rate-determining-step because of rather low dehydrogenation barrier for the α-hydrogen adsorption complex (thermodynamic control), while the hydroxyl path is determined by its dehydrogenation step (kinetic control). The effects of alloyed metal on the catalysis activity of Pt for ethanol partial oxidation, including adsorption energy, energy barrier, electronic structure, and eventually rate constant were discussed. Among all of the alloyed metals only Sn enhances the rate constant of the dehydrogenation via the α-hydrogen path on the Pt site of Pt3Sn as compared with Pt alone, which interprets why the PtSn is the most active to the oxidation of ethanol. PMID:22102920

Planning Under Uncertainty: Methods and Applications

DTIC Science & Technology

2010-06-09

begun research into fundamental algorithms for optimization and re?optimization of continuous optimization problems (such as linear and quadratic... algorithm yields a 14.3% improvement over the original design while saving 68.2 % of the simulation evaluations compared to standard sample-path...They provide tools for building and justifying computational algorithms for such problems. Year. 2010 Month: 03 Final Research under this grant

A real-time path rating calculation tool powered by HPC

DOE Office of Scientific and Technical Information (OSTI.GOV)

If transmission path ratings are determined in real time and optimized control methods can be implemented, congestion problems can be more effectively managed using the existing transmission assets, reducing congestion costs, avoiding capital expenditures for new physical assets, increasing revenues from the existing system, and maintaining reliability. In just one illustrative case, a BPA study has shown that a 1000-MW rating increase for a transmission path generates $15M in annual revenue, even if only 25% of the increased margin can be tapped for just 25% of the year.

Production of sugars and levulinic acid from marine biomass Gelidium amansii.

PubMed

Jeong, Gwi-Taek; Park, Don-Hee

2010-05-01

This study focused on optimization of reaction conditions for formation of sugars and levulinic acid from marine algal biomass Gelidium amansii using acid catalyst and by using statistical approach. By this approach, optimal conditions for production of sugars and levulinic acid were found as follows: glucose (reaction temperature of 139.4 degrees C, reaction time of 15.0 min, and catalyst concentration of 3.0%), galactose (108.2 degrees C, 45.0 min, and 3.0%), and levulinic acid (160.0 degrees C, 43.1 min, and 3.0%). While trying to optimize the conditions for the production of glucose and galactose, levulinic acid production was found to be minimum. Similarly, the production of glucose and galactose were found to be minimum while optimizing the conditions for the production of levulinic acid. In addition, optimized production of glucose required a higher reaction temperature and shorter reaction time than that of galactose. Levulinic acid was formed at a high reaction temperature, long reaction time, and high catalyst concentration. The combined results of this study may provide useful information to develop more economical and efficient systems for production of sugars and chemicals from marine biomass.

Discrete Particle Swarm Optimization Routing Protocol for Wireless Sensor Networks with Multiple Mobile Sinks.

PubMed

Yang, Jin; Liu, Fagui; Cao, Jianneng; Wang, Liangming

2016-07-14

Mobile sinks can achieve load-balancing and energy-consumption balancing across the wireless sensor networks (WSNs). However, the frequent change of the paths between source nodes and the sinks caused by sink mobility introduces significant overhead in terms of energy and packet delays. To enhance network performance of WSNs with mobile sinks (MWSNs), we present an efficient routing strategy, which is formulated as an optimization problem and employs the particle swarm optimization algorithm (PSO) to build the optimal routing paths. However, the conventional PSO is insufficient to solve discrete routing optimization problems. Therefore, a novel greedy discrete particle swarm optimization with memory (GMDPSO) is put forward to address this problem. In the GMDPSO, particle's position and velocity of traditional PSO are redefined under discrete MWSNs scenario. Particle updating rule is also reconsidered based on the subnetwork topology of MWSNs. Besides, by improving the greedy forwarding routing, a greedy search strategy is designed to drive particles to find a better position quickly. Furthermore, searching history is memorized to accelerate convergence. Simulation results demonstrate that our new protocol significantly improves the robustness and adapts to rapid topological changes with multiple mobile sinks, while efficiently reducing the communication overhead and the energy consumption.

Combined control-structure optimization

NASA Technical Reports Server (NTRS)

Salama, M.; Milman, M.; Bruno, R.; Scheid, R.; Gibson, S.

1989-01-01

An approach for combined control-structure optimization keyed to enhancing early design trade-offs is outlined and illustrated by numerical examples. The approach employs a homotopic strategy and appears to be effective for generating families of designs that can be used in these early trade studies. Analytical results were obtained for classes of structure/control objectives with linear quadratic Gaussian (LQG) and linear quadratic regulator (LQR) costs. For these, researchers demonstrated that global optima can be computed for small values of the homotopy parameter. Conditions for local optima along the homotopy path were also given. Details of two numerical examples employing the LQR control cost were given showing variations of the optimal design variables along the homotopy path. The results of the second example suggest that introducing a second homotopy parameter relating the two parts of the control index in the LQG/LQR formulation might serve to enlarge the family of Pareto optima, but its effect on modifying the optimal structural shapes may be analogous to the original parameter lambda.

Optimization for Service Routes of Pallet Service Center Based on the Pallet Pool Mode

PubMed Central

He, Shiwei; Song, Rui

2016-01-01

Service routes optimization (SRO) of pallet service center should meet customers' demand firstly and then, through the reasonable method of lines organization, realize the shortest path of vehicle driving. The routes optimization of pallet service center is similar to the distribution problems of vehicle routing problem (VRP) and Chinese postman problem (CPP), but it has its own characteristics. Based on the relevant research results, the conditions of determining the number of vehicles, the one way of the route, the constraints of loading, and time windows are fully considered, and a chance constrained programming model with stochastic constraints is constructed taking the shortest path of all vehicles for a delivering (recycling) operation as an objective. For the characteristics of the model, a hybrid intelligent algorithm including stochastic simulation, neural network, and immune clonal algorithm is designed to solve the model. Finally, the validity and rationality of the optimization model and algorithm are verified by the case. PMID:27528865

Equipartition terms in transition path ensemble: Insights from molecular dynamics simulations of alanine dipeptide.

PubMed

Li, Wenjin

2018-02-28

Transition path ensemble consists of reactive trajectories and possesses all the information necessary for the understanding of the mechanism and dynamics of important condensed phase processes. However, quantitative description of the properties of the transition path ensemble is far from being established. Here, with numerical calculations on a model system, the equipartition terms defined in thermal equilibrium were for the first time estimated in the transition path ensemble. It was not surprising to observe that the energy was not equally distributed among all the coordinates. However, the energies distributed on a pair of conjugated coordinates remained equal. Higher energies were observed to be distributed on several coordinates, which are highly coupled to the reaction coordinate, while the rest were almost equally distributed. In addition, the ensemble-averaged energy on each coordinate as a function of time was also quantified. These quantitative analyses on energy distributions provided new insights into the transition path ensemble.

Helicopter Pitch-Control Mechanism Reduces Vibration

NASA Technical Reports Server (NTRS)

Lemont, H.

1986-01-01

Large forces accommodated without increasing weight of helicopter structure. New mechanism yields stiffer control and improves accuracy of pitch changes under load. As result, heavy casting not for gearbox, nor extra reinforcing members needed for fuselage bulkheads, stringers, skin, and other parts. In new mechanism, reaction forces developed in rotor hub. Long load paths to gearbox and fuselage elminated. Reaction member rigidly attached to hub and rotates with it. At lower end of reaction member, bearing forms bridge to fuselage through stationary beam and antirotation link. Beam connected to reaction plate through rods.

Path planning algorithms for assembly sequence planning. [in robot kinematics

NASA Technical Reports Server (NTRS)

Krishnan, S. S.; Sanderson, Arthur C.

1991-01-01

Planning for manipulation in complex environments often requires reasoning about the geometric and mechanical constraints which are posed by the task. In planning assembly operations, the automatic generation of operations sequences depends on the geometric feasibility of paths which permit parts to be joined into subassemblies. Feasible locations and collision-free paths must be present for part motions, robot and grasping motions, and fixtures. This paper describes an approach to reasoning about the feasibility of straight-line paths among three-dimensional polyhedral parts using an algebra of polyhedral cones. A second method recasts the feasibility conditions as constraints in a nonlinear optimization framework. Both algorithms have been implemented and results are presented.

Rapid near-optimal trajectory generation and guidance law development for single-stage-to-orbit airbreathing vehicles

NASA Technical Reports Server (NTRS)

Calise, A. J.; Flandro, G. A.; Corban, J. E.

1990-01-01

General problems associated with on-board trajectory optimization, propulsion system cycle selection, and with the synthesis of guidance laws were addressed for an ascent to low-earth-orbit of an air-breathing single-stage-to-orbit vehicle. The NASA Generic Hypersonic Aerodynamic Model Example and the Langley Accelerator aerodynamic sets were acquired and implemented. Work related to the development of purely analytic aerodynamic models was also performed at a low level. A generic model of a multi-mode propulsion system was developed that includes turbojet, ramjet, scramjet, and rocket engine cycles. Provisions were made in the dynamic model for a component of thrust normal to the flight path. Computational results, which characterize the nonlinear sensitivity of scramjet performance to changes in vehicle angle of attack, were obtained and incorporated into the engine model. Additional trajectory constraints were introduced: maximum dynamic pressure; maximum aerodynamic heating rate per unit area; angle of attack and lift limits; and limits on acceleration both along and normal to the flight path. The remainder of the effort focused on required modifications to a previously derived algorithm when the model complexity cited above was added. In particular, analytic switching conditions were derived which, under appropriate assumptions, govern optimal transition from one propulsion mode to another for two cases: the case in which engine cycle operations can overlap, and the case in which engine cycle operations are mutually exclusive. The resulting guidance algorithm was implemented in software and exercised extensively. It was found that the approximations associated with the assumed time scale separation employed in this work are reasonable except over the Mach range from roughly 5 to 8. This phenomenon is due to the very large thrust capability of scramjets in this Mach regime when sized to meet the requirement for ascent to orbit. By accounting for flight path angle and flight path angle rate in construction of the flight path over this Mach range, the resulting algorithm provides the means for rapid near-optimal trajectory generation and propulsion cycle selection over the entire Mach range from take-off to orbit.

FACTOR - FACTOR II. Departmental Program and Model Documentation 71-3.

ERIC Educational Resources Information Center

Wilson, Stanley; Billingsley, Ray

This computer program is designed to optimize a Cobb-Douglas type of production function. The user of this program may choose isoquants and/or the expansion path for a Cobb-Douglas type of production function with up to nine resources. An expansion path is the combination of quantities of each resource that minimizes the cost at each production…

The most likely voltage path and large deviations approximations for integrate-and-fire neurons.

PubMed

Paninski, Liam

2006-08-01

We develop theory and numerical methods for computing the most likely subthreshold voltage path of a noisy integrate-and-fire (IF) neuron, given observations of the neuron's superthreshold spiking activity. This optimal voltage path satisfies a second-order ordinary differential (Euler-Lagrange) equation which may be solved analytically in a number of special cases, and which may be solved numerically in general via a simple "shooting" algorithm. Our results are applicable for both linear and nonlinear subthreshold dynamics, and in certain cases may be extended to correlated subthreshold noise sources. We also show how this optimal voltage may be used to obtain approximations to (1) the likelihood that an IF cell with a given set of parameters was responsible for the observed spike train; and (2) the instantaneous firing rate and interspike interval distribution of a given noisy IF cell. The latter probability approximations are based on the classical Freidlin-Wentzell theory of large deviations principles for stochastic differential equations. We close by comparing this most likely voltage path to the true observed subthreshold voltage trace in a case when intracellular voltage recordings are available in vitro.

Predictors of quality of life: A quantitative investigation of the stress-coping model in children with asthma

PubMed Central

Peeters, Yvette; Boersma, Sandra N; Koopman, Hendrik M

2008-01-01

Background Aim of this study is to further explore predictors of health related quality of life in children with asthma using factors derived from to the extended stress-coping model. While the stress-coping model has often been used as a frame of reference in studying health related quality of life in chronic illness, few have actually tested the model in children with asthma. Method In this survey study data were obtained by means of self-report questionnaires from seventy-eight children with asthma and their parents. Based on data derived from these questionnaires the constructs of the extended stress-coping model were assessed, using regression analysis and path analysis. Results The results of both regression analysis and path analysis reveal tentative support for the proposed relationships between predictors and health related quality of life in the stress-coping model. Moreover, as indicated in the stress-coping model, HRQoL is only directly predicted by coping. Both coping strategies 'emotional reaction' (significantly) and 'avoidance' are directly related to HRQoL. Conclusion In children with asthma, the extended stress-coping model appears to be a useful theoretical framework for understanding the impact of the illness on their quality of life. Consequently, the factors suggested by this model should be taken into account when designing optimal psychosocial-care interventions. PMID:18366753

Maximum cycle work output optimization for generalized radiative law Otto cycle engines

NASA Astrophysics Data System (ADS)

Xia, Shaojun; Chen, Lingen; Sun, Fengrui

2016-11-01

An Otto cycle internal combustion engine which includes thermal and friction losses is investigated by finite-time thermodynamics, and the optimization objective is the maximum cycle work output. The thermal energy transfer from the working substance to the cylinder inner wall follows the generalized radiative law (q∝Δ (Tn)). Under the condition that all of the fuel consumption, the compression ratio and the cycle period are given, the optimal piston trajectories for both the examples with unlimited and limited accelerations on every stroke are determined, and the cycle-period distribution among all strokes is also optimized. Numerical calculation results for the case of radiative law are provided and compared with those obtained for the cases of Newtonian law and linear phenomenological law. The results indicate that the optimal piston trajectory on each stroke contains three sections, which consist of an original maximum-acceleration and a terminal maximum-deceleration parts; for the case of radiative law, optimizing the piston motion path can achieve an improvement of more than 20% in both the cycle-work output and the second-law efficiency of the Otto cycle compared with the conventional near-sinusoidal operation, and heat transfer mechanisms have both qualitative and quantitative influences on the optimal paths of piston movements.

Integration of On-Column Chemical Reactions in Protein Characterization by Liquid Chromatography/Mass Spectrometry: Cross-Path Reactive Chromatography.

PubMed

Pawlowski, Jake W; Carrick, Ian; Kaltashov, Igor A

2018-01-16

Profiling of complex proteins by means of mass spectrometry (MS) frequently requires that certain chemical modifications of their covalent structure (e.g., reduction of disulfide bonds), be carried out prior to the MS or MS/MS analysis. Traditionally, these chemical reactions take place in the off-line mode to allow the excess reagents (the majority of which interfere with the MS measurements and degrade the analytical signal) to be removed from the protein solution prior to MS measurements. In addition to a significant increase in the analysis time, chemical reactions may result in a partial or full loss of the protein if the modifications adversely affect its stability, e.g,, making it prone to aggregation. In this work we present a new approach to solving this problem by carrying out the chemical reactions online using the reactive chromatography scheme on a size exclusion chromatography (SEC) platform with MS detection. This is achieved by using a cross-path reaction scheme, i.e., by delaying the protein injection onto the SEC column (with respect to the injection of the reagent plug containing a disulfide-reducing agent), which allows the chemical reactions to be carried out inside the column for a limited (and precisely controlled) period of time, while the two plugs overlap inside the column. The reduced protein elutes separately from the unconsumed reagents, allowing the signal suppression in ESI to be avoided and enabling sensitive MS detection. The new method is used to measure fucosylation levels of a plasma protein haptoglobin at the whole protein level following online reduction of disulfide-linked tetrameric species to monomeric units. The feasibility of top-down fragmentation of disulfide-containing proteins is also demonstrated using β 2 -microglobulin and a monoclonal antibody (mAb). The new online technique is both robust and versatile, as the cross-path scheme can be readily expanded to include multiple reactions in a single experiment (as demonstrated in this work by oxidatively labeling mAb on the column, followed by reduction of its disulfide bonds and MS analysis of the extent of oxidation within each chain of the molecule).

Development of Bicarbonate-Activated Peroxide as a Chemical and Biological Warfare Agent Decontaminant

DTIC Science & Technology

2006-06-30

may operate for certain substrates. The reaction of equation 1 proceeds with the intermediacy of CO2 as shown in Figure 1. Although it is well...competition between paths 5 and 6 will depend on the conditions and the nature of the substrate S. Note that figures, equations , etc. in the...1 shows the complete reaction scheme used to model the equilibration reaction at low temperature. Table 1 Kinetic equations and their

Dual path mechanism in the thermal reduction of graphene oxide.

PubMed

Larciprete, Rosanna; Fabris, Stefano; Sun, Tao; Lacovig, Paolo; Baraldi, Alessandro; Lizzit, Silvano

2011-11-02

Graphene is easily produced by thermally reducing graphene oxide. However, defect formation in the C network during deoxygenation compromises the charge carrier mobility in the reduced material. Understanding the mechanisms of the thermal reactions is essential for defining alternative routes able to limit the density of defects generated by carbon evolution. Here, we identify a dual path mechanism in the thermal reduction of graphene oxide driven by the oxygen coverage: at low surface density, the O atoms adsorbed as epoxy groups evolve as O(2) leaving the C network unmodified. At higher coverage, the formation of other O-containing species opens competing reaction channels, which consume the C backbone. We combined spectroscopic tools and ab initio calculations to probe the species residing on the surface and those released in the gas phase during heating and to identify reaction pathways and rate-limiting steps. Our results illuminate the current puzzling scenario of the low temperature gasification of graphene oxide.

Formation of alternating interfacial layers in Au-12Ge/Ni joints

PubMed Central

Lin, Shih-kang; Tsai, Ming-yueh; Tsai, Ping-chun; Hsu, Bo-hsun

2014-01-01

Au-Ge alloys are promising materials for high-power and high-frequency packaging, and Ni is frequently used as diffusion barriers. This study investigates interfacial reactions in Au-12Ge/Ni joints at 300°C and 400°C. For the reactions at 300°C, typical interfacial morphology was observed and the diffusion path was (Au) + (Ge)/NiGe/Ni5Ge3/Ni. However, an interesting phenomenon – the formation of (Au,Ni,Ge)/NiGe alternating layers – was observed for the reactions at 400°C. The diffusion path across the interface was liquid/(Au,Ni,Ge)/NiGe/···/(Au,Ni,Ge)/NiGe/Ni2Ge/Ni. The periodic thermodynamic instability at the NiGe/Ni2Ge interface caused the subsequent nucleation of new (Au,Ni,Ge)/NiGe pairs. The thermodynamic foundation and mechanism of formation of the alternating layers are elaborated in this paper. PMID:24690992

A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states

NASA Astrophysics Data System (ADS)

Nguyen, Trong-Nghia; Putikam, Raghunath; Lin, M. C.

2015-03-01

We have discovered a new and highly competitive product channel in the unimolecular decay process for small Criegee intermediates, CH2OO and anti/syn-CH3C(H)OO, occurring by intramolecular insertion reactions via a roaming-like transition state (TS) based on quantum-chemical calculations. Our results show that in the decomposition of CH2OO and anti-CH3C(H)OO, the predominant paths directly produce cis-HC(O)OH and syn-CH3C(O)OH acids with >110 kcal/mol exothermicities via loose roaming-like insertion TSs involving the terminal O atom and the neighboring C-H bonds. For syn-CH3C(H)OO, the major decomposition channel occurs by abstraction of a H atom from the CH3 group by the terminal O atom producing CH2C(H)O-OH. At 298 K, the intramolecular insertion process in CH2OO was found to be 600 times faster than the commonly assumed ring-closing reaction.

Importance of geometric phase effects in ultracold chemistry

DOE PAGES

Hazra, Jisha; Kendrick, Brian K.; Balakrishnan, Naduvalath

2015-08-28

Here, it is demonstrated that the inclusion of the geometric phase has an important effect on ultracold chemical reaction rates. The effect appears in rotationally and vibrationally resolved integral cross sections as well as cross sections summed over all product quantum states. The effect arises from interference between scattering amplitudes of two reaction pathways: a direct path and a looping path that encircle the conical intersection between the two lowest adiabatic electronic potential energy surfaces. It is magnified when the two scattering amplitudes have comparable magnitude and they scatter into the same angular region which occurs in the isotropic scatteringmore » characteristic of the ultracold regime (s-wave scattering). Results are presented for the O + OH → H + O 2 reaction for total angular momentum quantum number J = 0–5. Large geometric phase effects occur for collision energies below 0.1 K, but the effect vanishes at higher energies when contributions from different partial waves are included. It is also qualitatively demonstrated that the geometric phase effect can be modulated by applying an external electric field allowing the possibility of quantum control of chemical reactions in the ultracold regime. In this case, the geometric phase plays the role of a “quantum switch” which can turn the reaction “on” or “off”.« less

Comprehensive mechanism and structure-sensitivity of ethanol oxidation on platinum: new transition-state searching method for resolving the complex reaction network.

PubMed

Wang, Hui-Fang; Liu, Zhi-Pan

2008-08-20

Ethanol oxidation on Pt is a typical multistep and multiselectivity heterogeneous catalytic process. A comprehensive understanding of this fundamental reaction would greatly benefit design of catalysts for use in direct ethanol fuel cells and the degradation of biomass-derived oxygenates. In this work, the reaction network of ethanol oxidation on different Pt surfaces, including close-packed Pt{111}, stepped Pt{211}, and open Pt{100}, is explored thoroughly with an efficient reaction path searching method, which integrates our new transition-state searching technique with periodic density functional theory calculations. Our new technique enables the location of the transition state and saddle points for most surface reactions simply and efficiently by optimization of local minima. We show that the selectivity of ethanol oxidation on Pt depends markedly on the surface structure, which can be attributed to the structure-sensitivity of two key reaction steps: (i) the initial dehydrogenation of ethanol and (ii) the oxidation of acetyl (CH3CO). On open surface sites, ethanol prefers C-C bond cleavage via strongly adsorbed intermediates (CH2CO or CHCO), which leads to complete oxidation to CO2. However, only partial oxidizations to CH3CHO and CH3COOH occur on Pt{111}. Our mechanism points out that the open surface Pt{100} is the best facet to fully oxidize ethanol at low coverages, which sheds light on the origin of the remarkable catalytic performance of Pt tetrahexahedra nanocrystals found recently. The physical origin of the structure-selectivity is rationalized in terms of both thermodynamics and kinetics. Two fundamental quantities that dictate the selectivity of ethanol oxidation are identified: (i) the ability of surface metal atoms to bond with unsaturated C-containing fragments and (ii) the relative stability of hydroxyl at surface atop sites with respect to other sites.

Development of new UV-vis spectroscopic microwave-assisted method for determination of glucose in pharmaceutical samples

NASA Astrophysics Data System (ADS)

Mabood, Fazal; Hussain, Z.; Haq, H.; Arian, M. B.; Boqué, R.; Khan, K. M.; Hussain, K.; Jabeen, F.; Hussain, J.; Ahmed, M.; Alharasi, A.; Naureen, Z.; Hussain, H.; Khan, A.; Perveen, S.

2016-01-01

A new UV-Visible spectroscopic method assisted with microwave for the determination of glucose in pharmaceutical formulations was developed. In this study glucose solutions were oxidized by ammonium molybdate in the presence of microwave energy and reacted with aniline to produce a colored solution. Optimum conditions of the reaction including wavelength, temperature, and pH of the medium and relative concentration ratio of the reactants were investigated. It was found that the optimal wavelength for the reaction is 610 nm, the optimal reaction time is 80 s, the optimal reaction temperature is 160 °C, the optimal reaction pH is 4, and the optimal concentration ratio aniline/ammonium molybdate solution was found to be 1:1. The limits of detection and quantification of the method are 0.82 and 2.75 ppm for glucose solution, respectively. The use of microwaves improved the speed of the method while the use of aniline improved the sensitivity of the method by shifting the wavelength.

Dual stage potential field method for robotic path planning

NASA Astrophysics Data System (ADS)

Singh, Pradyumna Kumar; Parida, Pramod Kumar

2018-04-01

Path planning for autonomous mobile robots are the root for all autonomous mobile systems. Various methods are used for optimization of path to be followed by the autonomous mobile robots. Artificial potential field based path planning method is one of the most used methods for the researchers. Various algorithms have been proposed using the potential field approach. But in most of the common problems are encounters while heading towards the goal or target. i.e. local minima problem, zero potential regions problem, complex shaped obstacles problem, target near obstacle problem. In this paper we provide a new algorithm in which two types of potential functions are used one after another. The former one is to use to get the probable points and later one for getting the optimum path. In this algorithm we consider only the static obstacle and goal.

An avionics sensitivity study. Volume 1: Operational considerations

NASA Technical Reports Server (NTRS)

Scott, R. W.; Mcconkey, E. D.

1976-01-01

Equipment and operational concepts affecting aircraft in the terminal area are reported. Curved approach applications and modified climb and descent procedures for minimum fuel consumption are considered. The curved approach study involves the application of MLS guidance to enable execution of the current visual approach to Washington National Airport under instrument flight conditions. The operational significance and the flight path control requirements involved in the application of curved approach paths to this situation are considered. Alternative flight path control regimes are considered to achieve minimum fuel consumption subject to constraints related to air traffic control requirements, flight crew and passenger reactions, and airframe and powerplant limitations.

Conjugate gradient optimization programs for shuttle reentry

NASA Technical Reports Server (NTRS)

Powers, W. F.; Jacobson, R. A.; Leonard, D. A.

1972-01-01

Two computer programs for shuttle reentry trajectory optimization are listed and described. Both programs use the conjugate gradient method as the optimization procedure. The Phase 1 Program is developed in cartesian coordinates for a rotating spherical earth, and crossrange, downrange, maximum deceleration, total heating, and terminal speed, altitude, and flight path angle are included in the performance index. The programs make extensive use of subroutines so that they may be easily adapted to other atmospheric trajectory optimization problems.

Statistical evaluation of a project to estimate fish trajectories through the intakes of Kaplan hydropower turbines

NASA Astrophysics Data System (ADS)

Sutton, Virginia Kay

This paper examines statistical issues associated with estimating paths of juvenile salmon through the intakes of Kaplan turbines. Passive sensors, hydrophones, detecting signals from ultrasonic transmitters implanted in individual fish released into the preturbine region were used to obtain the information to estimate fish paths through the intake. Aim and location of the sensors affects the spatial region in which the transmitters can be detected, and formulas relating this region to sensor aiming directions are derived. Cramer-Rao lower bounds for the variance of estimators of fish location are used to optimize placement of each sensor. Finally, a statistical methodology is developed for analyzing angular data collected from optimally placed sensors.

Development of the PEBLebl Traveling Salesman Problem Computerized Testbed

ERIC Educational Resources Information Center

Mueller, Shane T.; Perelman, Brandon S.; Tan, Yin Yin; Thanasuan, Kejkaew

2015-01-01

The traveling salesman problem (TSP) is a combinatorial optimization problem that requires finding the shortest path through a set of points ("cities") that returns to the starting point. Because humans provide heuristic near-optimal solutions to Euclidean versions of the problem, it has sometimes been used to investigate human visual…

Algorithms for constructing optimal paths and statistical analysis of passenger traffic

NASA Astrophysics Data System (ADS)

Trofimov, S. P.; Druzhinina, N. G.; Trofimova, O. G.

2018-01-01

Several existing information systems of urban passenger transport (UPT) are considered. Author’s UPT network model is presented. To a passenger a new service is offered that is the best path from one stop to another stop at a specified time. The algorithm and software implementation for finding the optimal path are presented. The algorithm uses the current UPT schedule. The article also describes the algorithm of statistical analysis of trip payments by the electronic E-cards. The algorithm allows obtaining the density of passenger traffic during the day. This density is independent of the network topology and UPT schedules. The resulting density of the traffic flow can solve a number of practical problems. In particular, the forecast for the overflow of passenger transport in the «rush» hours, the quantitative comparison of different topologies transport networks, constructing of the best UPT timetable. The efficiency of the proposed integrated approach is demonstrated by the example of the model town with arbitrary dimensions.

Hop Optimization and Relay Node Selection in Multi-hop Wireless Ad-Hoc Networks

NASA Astrophysics Data System (ADS)

Li, Xiaohua(Edward)

In this paper we propose an efficient approach to determine the optimal hops for multi-hop ad hoc wireless networks. Based on the assumption that nodes use successive interference cancellation (SIC) and maximal ratio combining (MRC) to deal with mutual interference and to utilize all the received signal energy, we show that the signal-to-interference-plus-noise ratio (SINR) of a node is determined only by the nodes before it, not the nodes after it, along a packet forwarding path. Based on this observation, we propose an iterative procedure to select the relay nodes and to calculate the path SINR as well as capacity of an arbitrary multi-hop packet forwarding path. The complexity of the algorithm is extremely low, and scaling well with network size. The algorithm is applicable in arbitrarily large networks. Its performance is demonstrated as desirable by simulations. The algorithm can be helpful in analyzing the performance of multi-hop wireless networks.

AUCTION MECHANISMS FOR IMPLEMENTING TRADABLE NETWORK PERMIT MARKETS

NASA Astrophysics Data System (ADS)

Wada, Kentaro; Akamatsu, Takashi

This paper proposes a new auction mechanism for implementing the tradable network permit markets. Assuming that each user makes a trip from an origin to a destination along a path in a specific time period, we design an auction mechanism that enables each user to purchase a bundle of permits corresponding to a set of links in the user's preferred path. The objective of the proposed mechanism is to achieve a socially optimal state with minimal revelation of users' private information. In order to achieve this, the mechanism employs an evolutionary approach that has an auction phase and a path capacity adjustment phase, which are repeated on a day-to-day basis. We prove that the proposed mechanism has the following desirable properties: (1) truthful bidding is the dominant strategy for each user and (2) the proposed mechanism converges to an approximate socially optimal state in the sense that the achieved value of the social surplus reaches its maximum value when the number of users is large.

Rapid, parallel path planning by propagating wavefronts of spiking neural activity

PubMed Central

Ponulak, Filip; Hopfield, John J.

2013-01-01

Efficient path planning and navigation is critical for animals, robotics, logistics and transportation. We study a model in which spatial navigation problems can rapidly be solved in the brain by parallel mental exploration of alternative routes using propagating waves of neural activity. A wave of spiking activity propagates through a hippocampus-like network, altering the synaptic connectivity. The resulting vector field of synaptic change then guides a simulated animal to the appropriate selected target locations. We demonstrate that the navigation problem can be solved using realistic, local synaptic plasticity rules during a single passage of a wavefront. Our model can find optimal solutions for competing possible targets or learn and navigate in multiple environments. The model provides a hypothesis on the possible computational mechanisms for optimal path planning in the brain, at the same time it is useful for neuromorphic implementations, where the parallelism of information processing proposed here can fully be harnessed in hardware. PMID:23882213

Density functional theory study of ethylene partial oxidation on Ag 7 clusters

NASA Astrophysics Data System (ADS)

Yu, Hua-Gen

2006-11-01

The partial oxidation reaction of ethylene on neutral and anionic Ag 7 clusters has been studied using the BPW91 hybrid DFT method with the Stuttgart RSC97 relativistic pseudopotential for the 28-electron ionic core of Ag. The atomic oxygen reaction mechanism is mainly addressed. Results show that the reaction occurs via a stable oxametallacycle intermediate ( AgOCH4p, p = 0 or -1), but it involves small reaction barriers along the reaction path. The ZPE-corrected barrier heights are obtained as 0.7-6.5 kcal/mole. In addition, the structure and anionic effects of Ag 7 clusters are also discussed.

Ab initio reaction pathways for photodissociation and isomerization of nitromethane on four singlet potential energy surfaces with three roaming paths

NASA Astrophysics Data System (ADS)

Isegawa, Miho; Liu, Fengyi; Maeda, Satoshi; Morokuma, Keiji

2014-06-01

Photodissociation pathways of nitromethane following π → π* electronic excitation are reported. The potential energy surfaces for four lowest singlet states are explored, and structures of many intermediates, dissociation limits, transition states, and minimum energy conical intersections were determined using the automated searching algorism called the global reaction route mapping strategy. Geometries are finally optimized at CASSCF(14e,11o) level and energies are computed at CAS(14o,11e)PT2 level. The calculated preferable pathways and important products qualitatively explain experimental observations. The major photodissociation product CH3 and NO2 (2B2) is formed by direct dissociation from the S1 state. Important pathways involving S1 and S0 states for production of various dissociation products CH3NO + O (1D), CH3O(X2E) + NO (X2Π), CH2NO + OH, and CH2O + HNO, as well as various isomerization pathways have been identified. Three roaming processes also have been identified: the O atom roaming in O dissociation from CH3NO2, the OH radical roaming in OH dissociation from CH2N(O)(OH), and the NO roaming in NO dissociation from CH3ONO.

Ab initio reaction pathways for photodissociation and isomerization of nitromethane on four singlet potential energy surfaces with three roaming paths.

PubMed

Isegawa, Miho; Liu, Fengyi; Maeda, Satoshi; Morokuma, Keiji

2014-06-28

Photodissociation pathways of nitromethane following π → π(*) electronic excitation are reported. The potential energy surfaces for four lowest singlet states are explored, and structures of many intermediates, dissociation limits, transition states, and minimum energy conical intersections were determined using the automated searching algorism called the global reaction route mapping strategy. Geometries are finally optimized at CASSCF(14e,11o) level and energies are computed at CAS(14o,11e)PT2 level. The calculated preferable pathways and important products qualitatively explain experimental observations. The major photodissociation product CH3 and NO2 ((2)B2) is formed by direct dissociation from the S1 state. Important pathways involving S1 and S0 states for production of various dissociation products CH3NO + O ((1)D), CH3O(X(2)E) + NO (X(2)Π), CH2NO + OH, and CH2O + HNO, as well as various isomerization pathways have been identified. Three roaming processes also have been identified: the O atom roaming in O dissociation from CH3NO2, the OH radical roaming in OH dissociation from CH2N(O)(OH), and the NO roaming in NO dissociation from CH3ONO.

Advanced High Energy Density Secondary Batteries with Multi‐Electron Reaction Materials

PubMed Central

Luo, Rui; Huang, Yongxin; Li, Li

2016-01-01

Secondary batteries have become important for smart grid and electric vehicle applications, and massive effort has been dedicated to optimizing the current generation and improving their energy density. Multi‐electron chemistry has paved a new path for the breaking of the barriers that exist in traditional battery research and applications, and provided new ideas for developing new battery systems that meet energy density requirements. An in‐depth understanding of multi‐electron chemistries in terms of the charge transfer mechanisms occuring during their electrochemical processes is necessary and urgent for the modification of secondary battery materials and development of secondary battery systems. In this Review, multi‐electron chemistry for high energy density electrode materials and the corresponding secondary battery systems are discussed. Specifically, four battery systems based on multi‐electron reactions are classified in this review: lithium‐ and sodium‐ion batteries based on monovalent cations; rechargeable batteries based on the insertion of polyvalent cations beyond those of alkali metals; metal–air batteries, and Li–S batteries. It is noted that challenges still exist in the development of multi‐electron chemistries that must be overcome to meet the energy density requirements of different battery systems, and much effort has more effort to be devoted to this. PMID:27840796

Optimizing Department of Defense Acquisition Development Test and Evaluation Scheduling

DTIC Science & Technology

2015-06-01

CPM Critical Path Method DOD Department of Defense DT&E development test and evaluation EMD engineering and manufacturing development GAMS...these, including the Program Evaluation Review Technique (PERT), the Critical Path Method ( CPM ), and the resource- constrained project-scheduling...problem (RCPSP). These are of particular interest to this thesis as the current scheduling method uses elements of the PERT/ CPM , and the test

Pyrolysis Products Of Dimethyldichlorosilane

NASA Technical Reports Server (NTRS)

Cagliostro, D. E.; Riccitiello, S. R.; Carswell, M. G.

1990-01-01

Report describes experimental study of chemical reactions and chemical products of chemical-vapor deposition of silicon carbide from dimethyldichlorosilane. Topic important because it relates to current interest in lightweight refractory materials for use in advanced aircraft and spacecraft. Analyses showed that at temperature of 700 to 1,100 degrees C and contact time of about 1 minute, SiC forms by two chemical-reaction paths.

Reaction path of energetic materials using THOR code

NASA Astrophysics Data System (ADS)

Duraes, L.; Campos, J.; Portugal, A.

1997-07-01

The method of predicting reaction path, using a thermochemical computer code, named THOR, allows for isobar and isochor adiabatic combustion and CJ detonation regimes, the calculation of the composition and thermodynamic properties of reaction products of energetic materials. THOR code assumes the thermodynamic equilibria of all possible products, for the minimum Gibbs free energy, using a thermal equation of state (EoS). The used HL EoS is a new EoS developed in previous works. HL EoS is supported by a Boltzmann EoS, taking α =13.5 to the exponent of the intermolecular potential and θ=1.4 to the adimensional temperature. This code allows now the possibility of estimating various sets of reaction products, obtained successively by the decomposition of the original reacting compound, as a function of the released energy. Two case studies of thermal decomposition procedure were selected, described, calculated and discussed - Ammonium Nitrate based explosives and Nitromethane - because they are very known explosives and their equivalence ratio is respectively near and greater than the stoicheiometry. Predictions of detonation properties of other condensed explosives, as a function of energy release, present results in good correlation with experimental values.

Sputtering, Plasma Chemistry, and RF Sheath Effects in Low-Temperature and Fusion Plasma Modeling

NASA Astrophysics Data System (ADS)

Jenkins, Thomas G.; Kruger, Scott E.; McGugan, James M.; Pankin, Alexei Y.; Roark, Christine M.; Smithe, David N.; Stoltz, Peter H.

2016-09-01

A new sheath boundary condition has been implemented in VSim, a plasma modeling code which makes use of both PIC/MCC and fluid FDTD representations. It enables physics effects associated with DC and RF sheath formation - local sheath potential evolution, heat/particle fluxes, and sputtering effects on complex plasma-facing components - to be included in macroscopic-scale plasma simulations that need not resolve sheath scale lengths. We model these effects in typical ICRF antenna operation scenarios on the Alcator C-Mod fusion device, and present comparisons of our simulation results with experimental data together with detailed 3D animations of antenna operation. Complex low-temperature plasma chemistry modeling in VSim is facilitated by MUNCHKIN, a standalone python/C++/SQL code that identifies possible reaction paths for a given set of input species, solves 1D rate equations for the ensuing system's chemical evolution, and generates VSim input blocks with appropriate cross-sections/reaction rates. These features, as well as principal path analysis (to reduce the number of simulated chemical reactions while retaining accuracy) and reaction rate calculations from user-specified distribution functions, will also be demonstrated. Supported by the U.S. Department of Energy's SBIR program, Award DE-SC0009501.

A method for integrating and ranking the evidence for biochemical pathways by mining reactions from text

PubMed Central

Miwa, Makoto; Ohta, Tomoko; Rak, Rafal; Rowley, Andrew; Kell, Douglas B.; Pyysalo, Sampo; Ananiadou, Sophia

2013-01-01

Motivation: To create, verify and maintain pathway models, curators must discover and assess knowledge distributed over the vast body of biological literature. Methods supporting these tasks must understand both the pathway model representations and the natural language in the literature. These methods should identify and order documents by relevance to any given pathway reaction. No existing system has addressed all aspects of this challenge. Method: We present novel methods for associating pathway model reactions with relevant publications. Our approach extracts the reactions directly from the models and then turns them into queries for three text mining-based MEDLINE literature search systems. These queries are executed, and the resulting documents are combined and ranked according to their relevance to the reactions of interest. We manually annotate document-reaction pairs with the relevance of the document to the reaction and use this annotation to study several ranking methods, using various heuristic and machine-learning approaches. Results: Our evaluation shows that the annotated document-reaction pairs can be used to create a rule-based document ranking system, and that machine learning can be used to rank documents by their relevance to pathway reactions. We find that a Support Vector Machine-based system outperforms several baselines and matches the performance of the rule-based system. The success of the query extraction and ranking methods are used to update our existing pathway search system, PathText. Availability: An online demonstration of PathText 2 and the annotated corpus are available for research purposes at http://www.nactem.ac.uk/pathtext2/. Contact: makoto.miwa@manchester.ac.uk Supplementary information: Supplementary data are available at Bioinformatics online. PMID:23813008

Nonequilibrium thermodynamics and a fluctuation theorem for individual reaction steps in a chemical reaction network

NASA Astrophysics Data System (ADS)

Pal, Krishnendu; Das, Biswajit; Banerjee, Kinshuk; Gangopadhyay, Gautam

2015-09-01

We have introduced an approach to nonequilibrium thermodynamics of an open chemical reaction network in terms of the propensities of the individual elementary reactions and the corresponding reverse reactions. The method is a microscopic formulation of the dissipation function in terms of the relative entropy or Kullback-Leibler distance which is based on the analogy of phase space trajectory with the path of elementary reactions in a network of chemical process. We have introduced here a fluctuation theorem valid for each opposite pair of elementary reactions which is useful in determining the contribution of each sub-reaction on the nonequilibrium thermodynamics of overall reaction. The methodology is applied to an oligomeric enzyme kinetics at a chemiostatic condition that leads the reaction to a nonequilibrium steady state for which we have estimated how each step of the reaction is energy driven or entropy driven to contribute to the overall reaction.

Shortest path problem on a grid network with unordered intermediate points

NASA Astrophysics Data System (ADS)

Saw, Veekeong; Rahman, Amirah; Eng Ong, Wen

2017-10-01

We consider a shortest path problem with single cost factor on a grid network with unordered intermediate points. A two stage heuristic algorithm is proposed to find a feasible solution path within a reasonable amount of time. To evaluate the performance of the proposed algorithm, computational experiments are performed on grid maps of varying size and number of intermediate points. Preliminary results for the problem are reported. Numerical comparisons against brute forcing show that the proposed algorithm consistently yields solutions that are within 10% of the optimal solution and uses significantly less computation time.

Joint Video Stitching and Stabilization from Moving Cameras.

PubMed

Guo, Heng; Liu, Shuaicheng; He, Tong; Zhu, Shuyuan; Zeng, Bing; Gabbouj, Moncef

2016-09-08

In this paper, we extend image stitching to video stitching for videos that are captured for the same scene simultaneously by multiple moving cameras. In practice, videos captured under this circumstance often appear shaky. Directly applying image stitching methods for shaking videos often suffers from strong spatial and temporal artifacts. To solve this problem, we propose a unified framework in which video stitching and stabilization are performed jointly. Specifically, our system takes several overlapping videos as inputs. We estimate both inter motions (between different videos) and intra motions (between neighboring frames within a video). Then, we solve an optimal virtual 2D camera path from all original paths. An enlarged field of view along the virtual path is finally obtained by a space-temporal optimization that takes both inter and intra motions into consideration. Two important components of this optimization are that (1) a grid-based tracking method is designed for an improved robustness, which produces features that are distributed evenly within and across multiple views, and (2) a mesh-based motion model is adopted for the handling of the scene parallax. Some experimental results are provided to demonstrate the effectiveness of our approach on various consumer-level videos and a Plugin, named "Video Stitcher" is developed at Adobe After Effects CC2015 to show the processed videos.

The algorithm for duration acceleration of repetitive projects considering the learning effect

NASA Astrophysics Data System (ADS)

Chen, Hongtao; Wang, Keke; Du, Yang; Wang, Liwan

2018-03-01

Repetitive project optimization problem is common in project scheduling. Repetitive Scheduling Method (RSM) has many irreplaceable advantages in the field of repetitive projects. As the same or similar work is repeated, the proficiency of workers will be correspondingly low to high, and workers will gain experience and improve the efficiency of operations. This is learning effect. Learning effect is one of the important factors affecting the optimization results in repetitive project scheduling. This paper analyzes the influence of the learning effect on the controlling path in RSM from two aspects: one is that the learning effect changes the controlling path, the other is that the learning effect doesn't change the controlling path. This paper proposes corresponding methods to accelerate duration for different types of critical activities and proposes the algorithm for duration acceleration based on the learning effect in RSM. And the paper chooses graphical method to identity activities' types and considers the impacts of the learning effect on duration. The method meets the requirement of duration while ensuring the lowest acceleration cost. A concrete bridge construction project is given to verify the effectiveness of the method. The results of this study will help project managers understand the impacts of the learning effect on repetitive projects, and use the learning effect to optimize project scheduling.

Efficient and Adaptive Methods for Computing Accurate Potential Surfaces for Quantum Nuclear Effects: Applications to Hydrogen-Transfer Reactions.

PubMed

DeGregorio, Nicole; Iyengar, Srinivasan S

2018-01-09

We present two sampling measures to gauge critical regions of potential energy surfaces. These sampling measures employ (a) the instantaneous quantum wavepacket density, an approximation to the (b) potential surface, its (c) gradients, and (d) a Shannon information theory based expression that estimates the local entropy associated with the quantum wavepacket. These four criteria together enable a directed sampling of potential surfaces that appears to correctly describe the local oscillation frequencies, or the local Nyquist frequency, of a potential surface. The sampling functions are then utilized to derive a tessellation scheme that discretizes the multidimensional space to enable efficient sampling of potential surfaces. The sampled potential surface is then combined with four different interpolation procedures, namely, (a) local Hermite curve interpolation, (b) low-pass filtered Lagrange interpolation, (c) the monomial symmetrization approximation (MSA) developed by Bowman and co-workers, and (d) a modified Shepard algorithm. The sampling procedure and the fitting schemes are used to compute (a) potential surfaces in highly anharmonic hydrogen-bonded systems and (b) study hydrogen-transfer reactions in biogenic volatile organic compounds (isoprene) where the transferring hydrogen atom is found to demonstrate critical quantum nuclear effects. In the case of isoprene, the algorithm discussed here is used to derive multidimensional potential surfaces along a hydrogen-transfer reaction path to gauge the effect of quantum-nuclear degrees of freedom on the hydrogen-transfer process. Based on the decreased computational effort, facilitated by the optimal sampling of the potential surfaces through the use of sampling functions discussed here, and the accuracy of the associated potential surfaces, we believe the method will find great utility in the study of quantum nuclear dynamics problems, of which application to hydrogen-transfer reactions and hydrogen-bonded systems is demonstrated here.

A Networks Approach to Modeling Enzymatic Reactions.

PubMed

Imhof, P

2016-01-01

Modeling enzymatic reactions is a demanding task due to the complexity of the system, the many degrees of freedom involved and the complex, chemical, and conformational transitions associated with the reaction. Consequently, enzymatic reactions are not determined by precisely one reaction pathway. Hence, it is beneficial to obtain a comprehensive picture of possible reaction paths and competing mechanisms. By combining individually generated intermediate states and chemical transition steps a network of such pathways can be constructed. Transition networks are a discretized representation of a potential energy landscape consisting of a multitude of reaction pathways connecting the end states of the reaction. The graph structure of the network allows an easy identification of the energetically most favorable pathways as well as a number of alternative routes. © 2016 Elsevier Inc. All rights reserved.

A quantum chemical study for the multichannel reaction PH 2 + PH 2

NASA Astrophysics Data System (ADS)

Pimentel, André S.; Viana, Rommel B.

2007-04-01

The PH 2 + PH 2 multichannel reaction path was proposed in this study. The transition state that connects the reactants to cis-P 2H 2 isomer was found for the first time ever. This process is not allowed to occur at ordinary conditions because of its high energy barrier, 70 kcal mol -1. The PH 2 + PH 2 disproportionation to form the triplet PH 3 radical is an exothermic and spontaneous reaction. The PH 2 + PH 2 reaction may also form the P 2H 4 molecule in the absence of surfaces.

Efficient use of strong light for high photosynthetic productivity: interrelationships between the optical path, the optimal population density and cell-growth inhibition.

PubMed

Richmond, Amos; Cheng-Wu, Zhang; Zarmi, Yair

2003-07-01

The interrelationships between the optical path in flat plate reactors and photosynthetic productivity were elucidated. In preliminary works, a great surge in photosynthetic productivity was attained in flat plate photoreactors with an ultra short (e.g. 1.0 cm) optical path, in which extremely high culture density was facilitated by vigorous stirring and strong light. This surge in net photosynthetic efficiency was associated with a very significant increase in the optimal population density facilitated by the very short optical path (OP). A salient feature of these findings concerns the necessity to address growth inhibition (GI) which becomes increasingly manifested as cell concentration rises above a certain, species-specific, threshold (e.g. 1-2 billion cells of Nannochloropsis sp. ml(-1)). Indeed, ultrahigh cell density cultures may be established and sustained only if growth inhibition is continuously, or at least frequently, removed. Nannochloropsis culture from which GI was not removed, yielded 60 mg(-1) h(-1), yielding 260 mg l(-1) h(-1) when GI was removed. Two basic factors crucial for obtaining maximal photosynthetic productivity and efficiency in strong photon irradiance are defined: (1) areal cell density must be optimal, as high as possible (cell growth inhibition having been eliminated), insuring the average photon irradiance (I(av)) available per cell is falling at the end of the linear phase of the PI(av) curve, relating rate of photosynthesis to I(av), i.e. approximately photon irradiance per cell. (2) The light-dark (L-D) cycle period, which is determined by travel time of cells between the dark and the light volumes along the optical path, should be made as short as practically feasible, so as to approach, as much as possible the photosynthetic unit turnover time. This is obtainable in flat plate reactors by reducing the OP to as small a magnitude as is practically feasible.

Kinematic path planning for space-based robotics

NASA Astrophysics Data System (ADS)

Seereeram, Sanjeev; Wen, John T.

1998-01-01

Future space robotics tasks require manipulators of significant dexterity, achievable through kinematic redundancy and modular reconfigurability, but with a corresponding complexity of motion planning. Existing research aims for full autonomy and completeness, at the expense of efficiency, generality or even user friendliness. Commercial simulators require user-taught joint paths-a significant burden for assembly tasks subject to collision avoidance, kinematic and dynamic constraints. Our research has developed a Kinematic Path Planning (KPP) algorithm which bridges the gap between research and industry to produce a powerful and useful product. KPP consists of three key components: path-space iterative search, probabilistic refinement, and an operator guidance interface. The KPP algorithm has been successfully applied to the SSRMS for PMA relocation and dual-arm truss assembly tasks. Other KPP capabilities include Cartesian path following, hybrid Cartesian endpoint/intermediate via-point planning, redundancy resolution and path optimization. KPP incorporates supervisory (operator) input at any detail to influence the solution, yielding desirable/predictable paths for multi-jointed arms, avoiding obstacles and obeying manipulator limits. This software will eventually form a marketable robotic planner suitable for commercialization in conjunction with existing robotic CAD/CAM packages.

An Experiment of GMPLS-Based Dispersion Compensation Control over In-Field Fibers

NASA Astrophysics Data System (ADS)

Seno, Shoichiro; Horiuchi, Eiichi; Yoshida, Sota; Sugihara, Takashi; Onohara, Kiyoshi; Kamei, Misato; Baba, Yoshimasa; Kubo, Kazuo; Mizuochi, Takashi

As ROADMs (Reconfigurable Optical Add/Drop Multiplexers) are becoming widely used in metro/core networks, distributed control of wavelength paths by extended GMPLS (Generalized MultiProtocol Label Switching) protocols has attracted much attention. For the automatic establishment of an arbitrary wavelength path satisfying dynamic traffic demands over a ROADM or WXC (Wavelength Cross Connect)-based network, precise determination of chromatic dispersion over the path and optimized assignment of dispersion compensation capabilities at related nodes are essential. This paper reports an experiment over in-field fibers where GMPLS-based control was applied for the automatic discovery of chromatic dispersion, path computation, and wavelength path establishment with dynamic adjustment of variable dispersion compensation. The GMPLS-based control scheme, which the authors called GMPLS-Plus, extended GMPLS's distributed control architecture with attributes for automatic discovery, advertisement, and signaling of chromatic dispersion. In this experiment, wavelength paths with distances of 24km and 360km were successfully established and error-free data transmission was verified. The experiment also confirmed path restoration with dynamic compensation adjustment upon fiber failure.

Two betweenness centrality measures based on Randomized Shortest Paths

PubMed Central

Kivimäki, Ilkka; Lebichot, Bertrand; Saramäki, Jari; Saerens, Marco

2016-01-01

This paper introduces two new closely related betweenness centrality measures based on the Randomized Shortest Paths (RSP) framework, which fill a gap between traditional network centrality measures based on shortest paths and more recent methods considering random walks or current flows. The framework defines Boltzmann probability distributions over paths of the network which focus on the shortest paths, but also take into account longer paths depending on an inverse temperature parameter. RSP’s have previously proven to be useful in defining distance measures on networks. In this work we study their utility in quantifying the importance of the nodes of a network. The proposed RSP betweenness centralities combine, in an optimal way, the ideas of using the shortest and purely random paths for analysing the roles of network nodes, avoiding issues involving these two paradigms. We present the derivations of these measures and how they can be computed in an efficient way. In addition, we show with real world examples the potential of the RSP betweenness centralities in identifying interesting nodes of a network that more traditional methods might fail to notice. PMID:26838176

Dynamic optimal strategies in transboundary pollution game under learning by doing

NASA Astrophysics Data System (ADS)

Chang, Shuhua; Qin, Weihua; Wang, Xinyu

2018-01-01

In this paper, we present a transboundary pollution game, in which emission permits trading and pollution abatement costs under learning by doing are considered. In this model, the abatement cost mainly depends on the level of pollution abatement and the experience of using pollution abatement technology. We use optimal control theory to investigate the optimal emission paths and the optimal pollution abatement strategies under cooperative and noncooperative games, respectively. Additionally, the effects of parameters on the results have been examined.

Discrete Particle Swarm Optimization Routing Protocol for Wireless Sensor Networks with Multiple Mobile Sinks

PubMed Central

Yang, Jin; Liu, Fagui; Cao, Jianneng; Wang, Liangming

2016-01-01

Mobile sinks can achieve load-balancing and energy-consumption balancing across the wireless sensor networks (WSNs). However, the frequent change of the paths between source nodes and the sinks caused by sink mobility introduces significant overhead in terms of energy and packet delays. To enhance network performance of WSNs with mobile sinks (MWSNs), we present an efficient routing strategy, which is formulated as an optimization problem and employs the particle swarm optimization algorithm (PSO) to build the optimal routing paths. However, the conventional PSO is insufficient to solve discrete routing optimization problems. Therefore, a novel greedy discrete particle swarm optimization with memory (GMDPSO) is put forward to address this problem. In the GMDPSO, particle’s position and velocity of traditional PSO are redefined under discrete MWSNs scenario. Particle updating rule is also reconsidered based on the subnetwork topology of MWSNs. Besides, by improving the greedy forwarding routing, a greedy search strategy is designed to drive particles to find a better position quickly. Furthermore, searching history is memorized to accelerate convergence. Simulation results demonstrate that our new protocol significantly improves the robustness and adapts to rapid topological changes with multiple mobile sinks, while efficiently reducing the communication overhead and the energy consumption. PMID:27428971

Thermodynamic Predictions vs. Measured Fluid Chemistry: Lessons from Low-Temperature, Serpentinizing Fluids

NASA Astrophysics Data System (ADS)

Leong, J. M.; Howells, A. H.; Robinson, K. J.; Shock, E. L.

2018-05-01

A combination of reaction-path, mixing, and sensitivity calculations was used to reconcile deviations between thermodynamic predictions and actual measurements of low-temperature serpentinizing fluid chemistry.

An automated integration-free path-integral method based on Kleinert's variational perturbation theory

NASA Astrophysics Data System (ADS)

Wong, Kin-Yiu; Gao, Jiali

2007-12-01

Based on Kleinert's variational perturbation (KP) theory [Path Integrals in Quantum Mechanics, Statistics, Polymer Physics, and Financial Markets, 3rd ed. (World Scientific, Singapore, 2004)], we present an analytic path-integral approach for computing the effective centroid potential. The approach enables the KP theory to be applied to any realistic systems beyond the first-order perturbation (i.e., the original Feynman-Kleinert [Phys. Rev. A 34, 5080 (1986)] variational method). Accurate values are obtained for several systems in which exact quantum results are known. Furthermore, the computed kinetic isotope effects for a series of proton transfer reactions, in which the potential energy surfaces are evaluated by density-functional theory, are in good accordance with experiments. We hope that our method could be used by non-path-integral experts or experimentalists as a "black box" for any given system.

Tortuous path chemical preconcentrator

DOEpatents

Manginell, Ronald P.; Lewis, Patrick R.; Adkins, Douglas R.; Wheeler, David R.; Simonson, Robert J.

2010-09-21

A non-planar, tortuous path chemical preconcentrator has a high internal surface area having a heatable sorptive coating that can be used to selectively collect and concentrate one or more chemical species of interest from a fluid stream that can be rapidly released as a concentrated plug into an analytical or microanalytical chain for separation and detection. The non-planar chemical preconcentrator comprises a sorptive support structure having a tortuous flow path. The tortuosity provides repeated twists, turns, and bends to the flow, thereby increasing the interfacial contact between sample fluid stream and the sorptive material. The tortuous path also provides more opportunities for desorption and readsorption of volatile species. Further, the thermal efficiency of the tortuous path chemical preconcentrator is comparable or superior to the prior non-planar chemical preconcentrator. Finally, the tortuosity can be varied in different directions to optimize flow rates during the adsorption and desorption phases of operation of the preconcentrator.

Efficient computation paths for the systematic analysis of sensitivities

NASA Astrophysics Data System (ADS)

Greppi, Paolo; Arato, Elisabetta

2013-01-01

A systematic sensitivity analysis requires computing the model on all points of a multi-dimensional grid covering the domain of interest, defined by the ranges of variability of the inputs. The issues to efficiently perform such analyses on algebraic models are handling solution failures within and close to the feasible region and minimizing the total iteration count. Scanning the domain in the obvious order is sub-optimal in terms of total iterations and is likely to cause many solution failures. The problem of choosing a better order can be translated geometrically into finding Hamiltonian paths on certain grid graphs. This work proposes two paths, one based on a mixed-radix Gray code and the other, a quasi-spiral path, produced by a novel heuristic algorithm. Some simple, easy-to-visualize examples are presented, followed by performance results for the quasi-spiral algorithm and the practical application of the different paths in a process simulation tool.

Rationalizing spatial exploration patterns of wild animals and humans through a temporal discounting framework.

PubMed

Namboodiri, Vijay Mohan K; Levy, Joshua M; Mihalas, Stefan; Sims, David W; Hussain Shuler, Marshall G

2016-08-02

Understanding the exploration patterns of foragers in the wild provides fundamental insight into animal behavior. Recent experimental evidence has demonstrated that path lengths (distances between consecutive turns) taken by foragers are well fitted by a power law distribution. Numerous theoretical contributions have posited that "Lévy random walks"-which can produce power law path length distributions-are optimal for memoryless agents searching a sparse reward landscape. It is unclear, however, whether such a strategy is efficient for cognitively complex agents, from wild animals to humans. Here, we developed a model to explain the emergence of apparent power law path length distributions in animals that can learn about their environments. In our model, the agent's goal during search is to build an internal model of the distribution of rewards in space that takes into account the cost of time to reach distant locations (i.e., temporally discounting rewards). For an agent with such a goal, we find that an optimal model of exploration in fact produces hyperbolic path lengths, which are well approximated by power laws. We then provide support for our model by showing that humans in a laboratory spatial exploration task search space systematically and modify their search patterns under a cost of time. In addition, we find that path length distributions in a large dataset obtained from free-ranging marine vertebrates are well described by our hyperbolic model. Thus, we provide a general theoretical framework for understanding spatial exploration patterns of cognitively complex foragers.

A novel communication mechanism based on node potential multi-path routing

NASA Astrophysics Data System (ADS)

Bu, Youjun; Zhang, Chuanhao; Jiang, YiMing; Zhang, Zhen

2016-10-01

With the network scales rapidly and new network applications emerge frequently, bandwidth supply for today's Internet could not catch up with the rapid increasing requirements. Unfortunately, irrational using of network sources makes things worse. Actual network deploys single-next-hop optimization paths for data transmission, but such "best effort" model leads to the imbalance use of network resources and usually leads to local congestion. On the other hand Multi-path routing can use the aggregation bandwidth of multi paths efficiently and improve the robustness of network, security, load balancing and quality of service. As a result, multi-path has attracted much attention in the routing and switching research fields and many important ideas and solutions have been proposed. This paper focuses on implementing the parallel transmission of multi next-hop data, balancing the network traffic and reducing the congestion. It aimed at exploring the key technologies of the multi-path communication network, which could provide a feasible academic support for subsequent applications of multi-path communication networking. It proposed a novel multi-path algorithm based on node potential in the network. And the algorithm can fully use of the network link resource and effectively balance network link resource utilization.

Transition path time distributions for Lévy flights

NASA Astrophysics Data System (ADS)

Janakiraman, Deepika

2018-07-01

This paper presents a study of transition path time distributions for Lévy noise-induced barrier crossing. Transition paths are short segments of the reactive trajectories and span the barrier region of the potential without spilling into the reactant/product wells. The time taken to traverse this segment is referred to as the transition path time. Since the transition path is devoid of excursions in the minimum, the corresponding time will give the exclusive barrier crossing time, unlike . This work explores the distribution of transition path times for superdiffusive barrier crossing, analytically. This is made possible by approximating the barrier by an inverted parabola. Using this approximation, the distributions are evaluated in both over- and under-damped limits of friction. The short-time behaviour of the distributions, provide analytical evidence for single-step transition events—a feature in Lévy-barrier crossing as observed in prior simulation studies. The average transition path time is calculated as a function of the Lévy index (α), and the optimal value of α leading to minimum average transition path time is discussed, in both the limits of friction. Langevin dynamics simulations corroborating with the analytical results are also presented.

Optimization and planning of operating theatre activities: an original definition of pathways and process modeling.

PubMed

Barbagallo, Simone; Corradi, Luca; de Ville de Goyet, Jean; Iannucci, Marina; Porro, Ivan; Rosso, Nicola; Tanfani, Elena; Testi, Angela

2015-05-17

The Operating Room (OR) is a key resource of all major hospitals, but it also accounts for up 40% of resource costs. Improving cost effectiveness, while maintaining a quality of care, is a universal objective. These goals imply an optimization of planning and a scheduling of the activities involved. This is highly challenging due to the inherent variable and unpredictable nature of surgery. A Business Process Modeling Notation (BPMN 2.0) was used for the representation of the "OR Process" (being defined as the sequence of all of the elementary steps between "patient ready for surgery" to "patient operated upon") as a general pathway ("path"). The path was then both further standardized as much as possible and, at the same time, keeping all of the key-elements that would allow one to address or define the other steps of planning, and the inherent and wide variability in terms of patient specificity. The path was used to schedule OR activity, room-by-room, and day-by-day, feeding the process from a "waiting list database" and using a mathematical optimization model with the objective of ending up in an optimized planning. The OR process was defined with special attention paid to flows, timing and resource involvement. Standardization involved a dynamics operation and defined an expected operating time for each operation. The optimization model has been implemented and tested on real clinical data. The comparison of the results reported with the real data, shows that by using the optimization model, allows for the scheduling of about 30% more patients than in actual practice, as well as to better exploit the OR efficiency, increasing the average operating room utilization rate up to 20%. The optimization of OR activity planning is essential in order to manage the hospital's waiting list. Optimal planning is facilitated by defining the operation as a standard pathway where all variables are taken into account. By allowing a precise scheduling, it feeds the process of planning and, further up-stream, the management of a waiting list in an interactive and bi-directional dynamic process.

Comparative dynamics in a health investment model.

PubMed

Eisenring, C

1999-10-01

The method of comparative dynamics fully exploits the inter-temporal structure of optimal control models. I derive comparative dynamic results in a simplified demand for health model. The effect of a change in the depreciation rate on the optimal paths for health capital and investment in health is studied by use of a phase diagram.

Longitudinal Examination of Optimism, Personal Self-Efficacy and Student Well-Being: A Path Analysis

ERIC Educational Resources Information Center

Phan, Huy P.

2016-01-01

The present longitudinal study, based on existing theoretical tenets, explored a conceptual model that depicted four major orientations: optimism, self-efficacy, and academic well-being. An important question for consideration, in this case, involved the testing of different untested trajectories that could explain and predict individuals'…

Bioreactor performance: a more scientific approach for practice.

PubMed

Lübbert, A; Bay Jørgensen, S

2001-02-13

In practice, the performance of a biochemical conversion process, i.e. the bioreactor performance, is essentially determined by the benefit/cost ratio. The benefit is generally defined in terms of the amount of the desired product produced and its market price. Cost reduction is the major objective in biochemical engineering. There are two essential engineering approaches to minimizing the cost of creating a particular product in an existing plant. One is to find a control path or operational procedure that optimally uses the dynamics of the process and copes with the many constraints restricting production. The other is to remove or lower the constraints by constructive improvements of the equipment and/or the microorganisms. This paper focuses on the first approach, dealing with optimization of the operational procedure and the measures by which one can ensure that the process adheres to the predetermined path. In practice, feedforward control is the predominant control mode applied. However, as it is frequently inadequate for optimal performance, feedback control may also be employed. Relevant aspects of such performance optimization are discussed.