Sample records for reaction path models

  1. Geochemical controls on shale groundwaters: Results of reaction path modeling

    Von Damm, K.L.; VandenBrook, A.J.


    The EQ3NR/EQ6 geochemical modeling code was used to simulate the reaction of several shale mineralogies with different groundwater compositions in order to elucidate changes that may occur in both the groundwater compositions, and rock mineralogies and compositions under conditions which may be encountered in a high-level radioactive waste repository. Shales with primarily illitic or smectitic compositions were the focus of this study. The reactions were run at the ambient temperatures of the groundwaters and to temperatures as high as 250/degree/C, the approximate temperature maximum expected in a repository. All modeling assumed that equilibrium was achieved and treated the rock and water assemblage as a closed system. Graphite was used as a proxy mineral for organic matter in the shales. The results show that the presence of even a very small amount of reducing mineral has a large influence on the redox state of the groundwaters, and that either pyrite or graphite provides essentially the same results, with slight differences in dissolved C, Fe and S concentrations. The thermodynamic data base is inadequate at the present time to fully evaluate the speciation of dissolved carbon, due to the paucity of thermodynamic data for organic compounds. In the illitic cases the groundwaters resulting from interaction at elevated temperatures are acid, while the smectitic cases remain alkaline, although the final equilibrium mineral assemblages are quite similar. 10 refs., 8 figs., 15 tabs.

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

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


    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.

  3. Parallel iterative reaction path optimization in ab initio quantum mechanical/molecular mechanical modeling of enzyme reactions.

    Liu, Haiyan; Lu, Zhenyu; Cisneros, G Andres; Yang, Weitao


    The determination of reaction paths for enzyme systems remains a great challenge for current computational methods. In this paper we present an efficient method for the determination of minimum energy reaction paths with the ab initio quantum mechanical/molecular mechanical approach. Our method is based on an adaptation of the path optimization procedure by Ayala and Schlegel for small molecules in gas phase, the iterative quantum mechanical/molecular mechanical (QM/MM) optimization method developed earlier in our laboratory and the introduction of a new metric defining the distance between different structures in the configuration space. In this method we represent the reaction path by a discrete set of structures. For each structure we partition the atoms into a core set that usually includes the QM subsystem and an environment set that usually includes the MM subsystem. These two sets are optimized iteratively: the core set is optimized to approximate the reaction path while the environment set is optimized to the corresponding energy minimum. In the optimization of the core set of atoms for the reaction path, we introduce a new metric to define the distances between the points on the reaction path, which excludes the soft degrees of freedom from the environment set and includes extra weights on coordinates describing chemical changes. Because the reaction path is represented by discrete structures and the optimization for each can be performed individually with very limited coupling, our method can be executed in a natural and efficient parallelization, with each processor handling one of the structures. We demonstrate the applicability and efficiency of our method by testing it on two systems previously studied by our group, triosephosphate isomerase and 4-oxalocrotonate tautomerase. In both cases the minimum energy paths for both enzymes agree with the previously reported paths.

  4. On the Reaction Path Hamiltonian

    孙家钟; 李泽生


    A vector-fiber bundle structure of the reaction path Hamiltonian, which has been introduced by Miller, Handy and Adams, is explored with respect to molecular vibrations orthogonal to the reaction path. The symmetry of the fiber bundle is characterized by the real orthogonal group O(3N- 7) for the dynamical system with N atoms. Under the action of group O(3N- 7). the kinetic energy of the reaction path Hamiltonian is left invariant. Furthermore , the invariant behaviour of the Hamiltonian vector fields is investigated.

  5. Chemical reaction path modeling of hydrothermal processes on Mars: Preliminary results

    Plumlee, Geoffrey S.; Ridley, W. Ian


    Hydrothermal processes are thought to have had significant roles in the development of surficial mineralogies and morphological features on Mars. For example, a significant proportion of the Martian soil could consist of the erosional products of hydrothermally altered impact melt sheets. In this model, impact-driven, vapor-dominated hydrothermal systems hydrothermally altered the surrounding rocks and transported volatiles such as S and Cl to the surface. Further support for impact-driven hydrothermal alteration on Mars was provided by studies of the Ries crater, Germany, where suevite deposits were extensively altered to montmorillonite clays by inferred low-temperature (100-130 C) hydrothermal fluids. It was also suggested that surface outflow from both impact-driven and volcano-driven hydrothermal systems could generate the valley networks, thereby eliminating the need for an early warm wet climate. We use computer-driven chemical reaction path calculation to model chemical processes which were likely associated with postulated Martian hydrothermal systems.

  6. Improved Geothermometry Through Multivariate Reaction-path Modeling and Evaluation of Geomicrobiological Influences on Geochemical Temperature Indicators: Final Report

    Mattson, Earl [Idaho National Lab. (INL), Idaho Falls, ID (United States); Smith, Robert [Idaho National Lab. (INL), Idaho Falls, ID (United States); Fujita, Yoshiko [Idaho National Lab. (INL), Idaho Falls, ID (United States); McLing, Travis [Idaho National Lab. (INL), Idaho Falls, ID (United States); Neupane, Ghanashyam [Idaho National Lab. (INL), Idaho Falls, ID (United States); Palmer, Carl [Idaho National Lab. (INL), Idaho Falls, ID (United States); Reed, David [Idaho National Lab. (INL), Idaho Falls, ID (United States); Thompson, Vicki [Idaho National Lab. (INL), Idaho Falls, ID (United States)


    The project was aimed at demonstrating that the geothermometric predictions can be improved through the application of multi-element reaction path modeling that accounts for lithologic and tectonic settings, while also accounting for biological influences on geochemical temperature indicators. The limited utilization of chemical signatures by individual traditional geothermometer in the development of reservoir temperature estimates may have been constraining their reliability for evaluation of potential geothermal resources. This project, however, was intended to build a geothermometry tool which can integrate multi-component reaction path modeling with process-optimization capability that can be applied to dilute, low-temperature water samples to consistently predict reservoir temperature within ±30 °C. The project was also intended to evaluate the extent to which microbiological processes can modulate the geochemical signals in some thermal waters and influence the geothermometric predictions.

  7. Analyzing Complex Reaction Mechanisms Using Path Sampling.

    van Erp, Titus S; Moqadam, Mahmoud; Riccardi, Enrico; Lervik, Anders


    We introduce an approach to analyze collective variables (CVs) regarding their predictive power for a reaction. The method is based on already available path sampling data produced by, for instance, transition interface sampling or forward flux sampling, which are path sampling methods used for efficient computation of reaction rates. By a search in CV space, a measure of predictiveness can be optimized and, in addition, the number of CVs can be reduced using projection operations which keep this measure invariant. The approach allows testing hypotheses on the reaction mechanism but could, in principle, also be used to construct the phase-space committor surfaces without the need of additional trajectory sampling. The procedure is illustrated for a one-dimensional double-well potential, a theoretical model for an ion-transfer reaction in which the solvent structure can lower the barrier, and an ab initio molecular dynamics study of water auto-ionization. The analysis technique enhances the quantitative interpretation of path sampling data which can provide clues on how chemical reactions can be steered in desired directions.

  8. Reaction path synthesis methodology for waste minimization

    HU; Shanying; LI; Mingheng; LI; Yourun; SHEN; Jingzhu; LIU


    It is a key step for reducing waste generation in chemical processes to design optimal reaction paths. In this paper, methods of waste minimization for reaction path synthesis problems are proposed to realize eco-industrial production mode with minimum waste emission. A new conception of simple stoichiometric reaction is presented for reaction path synthesis problem. All simple stoichiometric reactions can be obtained by mathematical transformation for atom matrix of a reaction system. Based on the conception, a two-tier optimization method for complex reaction path synthesis problems is addressed. The first step is to determine the economic optimal overall reactions, and the second step to decompose each overall reaction into several sub-reactions and find out the best thermodynamic feasible reaction path. Further, a method of reaction path synthesis with waste closed-cycle is proposed based on simple stoichiometric reactions for achieving zero waste emission to poly-generation problem of multi-products. Case studies show that the proposed methods can efficiently solve practical reaction path synthesis problems.

  9. Variational path-integral approach to back-reactions of composite mesons in the Nambu-Jona-Lasinio model

    Blaschke, D.; Ebert, D.


    For the investigation of back-reactions of composite mesons in the NJL model, a variational path-integral treatment is formulated which yields an effective action Aeff [Dσ ,Dπ ; S ], depending on the propagators Dσ, Dπ of σ- and π-mesons and on the full quark propagator S. The stationarity conditions δAeff / δS = 0, δAeff / δDσ = 0, δAeff / δDπ = 0, then lead to coupled Schwinger-Dyson (SD) equations for the quark self-energy and the meson polarization functions. These results reproduce and extend results of the so-called ;Φ-derivable; approach and provide a functional formulation for diagrammatic resummations of 1 /Nc -corrections in the NJL model. Finally, we perform a low-momentum estimate of the quark and meson loop contributions to the polarization function of the pion and on this basis discuss the Goldstone theorem.

  10. Modeling stopped-flow data for nucleic acid duplex formation reactions: the importance of off-path intermediates.

    Sikora, Jacqueline R; Rauzan, Brittany; Stegemann, Rachel; Deckert, Alice


    Evidence for unexpected off-path intermediates to DNA duplex formation is presented. These off-path intermediates are shown to involve unimolecular and, in one case, bimolecular structure in one of the single strands of complementary DNA. Three models are developed to account for the observed single-stranded structures that are formed in parallel with duplex formation. These models are applied to the analysis of stopped-flow data for eight different nonself-complementary duplex formation reactions in order to extract the elementary rate constant for formation of the duplex from the complementary random coil single-stranded DNA. The free energy of activation (at 25 °C) for the denaturation of each duplex is calculated from these data and is shown to have a linear correlation to the overall standard free energy for duplex formation (also at 25 °C). Duplexes that contain mismatches obey a parallel linear free-energy (LFE) relationship with a y-intercept that is greater than that of duplexes without mismatches. Slopes near unity for the LFE relationships indicate that all duplexes go through an early, unstructured transition state.

  11. An interactive code (NETPATH) for modeling NET geochemical reactions along a flow PATH, version 2.0

    Plummer, L. Niel; Prestemon, Eric C.; Parkhurst, David L.


    NETPATH is an interactive Fortran 77 computer program used to interpret net geochemical mass-balance reactions between an initial and final water along a hydrologic flow path. Alternatively, NETPATH computes the mixing proportions of two to five initial waters and net geochemical reactions that can account for the observed composition of a final water. The program utilizes previously defined chemical and isotopic data for waters from a hydrochemical system. For a set of mineral and (or) gas phases hypothesized to be the reactive phases in the system, NETPATH calculates the mass transfers in every possible combination of the selected phases that accounts for the observed changes in the selected chemical and (or) isotopic compositions observed along the flow path. The calculations are of use in interpreting geochemical reactions, mixing proportions, evaporation and (or) dilution of waters, and mineral mass transfer in the chemical and isotopic evolution of natural and environmental waters. Rayleigh distillation calculations are applied to each mass-balance model that satisfies the constraints to predict carbon, sulfur, nitrogen, and strontium isotopic compositions at the end point, including radiocarbon dating. DB is an interactive Fortran 77 computer program used to enter analytical data into NETPATH, and calculate the distribution of species in aqueous solution. This report describes the types of problems that can be solved, the methods used to solve problems, and the features available in the program to facilitate these solutions. Examples are presented to demonstrate most of the applications and features of NETPATH. The codes DB and NETPATH can be executed in the UNIX or DOS1 environment. This report replaces U.S. Geological Survey Water-Resources Investigations Report 91-4078, by Plummer and others, which described the original release of NETPATH, version 1.0 (dated December, 1991), and documents revisions and enhancements that are included in version 2.0. 1 The

  12. EQ6, a computer program for reaction path modeling of aqueous geochemical systems: Theoretical manual, user`s guide, and related documentation (Version 7.0); Part 4

    Wolery, T.J.; Daveler, S.A.


    EQ6 is a FORTRAN computer program in the EQ3/6 software package (Wolery, 1979). It calculates reaction paths (chemical evolution) in reacting water-rock and water-rock-waste systems. Speciation in aqueous solution is an integral part of these calculations. EQ6 computes models of titration processes (including fluid mixing), irreversible reaction in closed systems, irreversible reaction in some simple kinds of open systems, and heating or cooling processes, as well as solve ``single-point`` thermodynamic equilibrium problems. A reaction path calculation normally involves a sequence of thermodynamic equilibrium calculations. Chemical evolution is driven by a set of irreversible reactions (i.e., reactions out of equilibrium) and/or changes in temperature and/or pressure. These irreversible reactions usually represent the dissolution or precipitation of minerals or other solids. The code computes the appearance and disappearance of phases in solubility equilibrium with the water. It finds the identities of these phases automatically. The user may specify which potential phases are allowed to form and which are not. There is an option to fix the fugacities of specified gas species, simulating contact with a large external reservoir. Rate laws for irreversible reactions may be either relative rates or actual rates. If any actual rates are used, the calculation has a time frame. Several forms for actual rate laws are programmed into the code. EQ6 is presently able to model both mineral dissolution and growth kinetics.

  13. PATHS groundwater hydrologic model

    Nelson, R.W.; Schur, J.A.


    A preliminary evaluation capability for two-dimensional groundwater pollution problems was developed as part of the Transport Modeling Task for the Waste Isolation Safety Assessment Program (WISAP). Our approach was to use the data limitations as a guide in setting the level of modeling detail. PATHS Groundwater Hydrologic Model is the first level (simplest) idealized hybrid analytical/numerical model for two-dimensional, saturated groundwater flow and single component transport; homogeneous geology. This document consists of the description of the PATHS groundwater hydrologic model. The preliminary evaluation capability prepared for WISAP, including the enhancements that were made because of the authors' experience using the earlier capability is described. Appendixes A through D supplement the report as follows: complete derivations of the background equations are provided in Appendix A. Appendix B is a comprehensive set of instructions for users of PATHS. It is written for users who have little or no experience with computers. Appendix C is for the programmer. It contains information on how input parameters are passed between programs in the system. It also contains program listings and test case listing. Appendix D is a definition of terms.

  14. Deciphering P-T-t Paths from Reaction Microstructures in Metamorphic Rocks: a New Approach by Means of Three-Dimensional Finite Element Modelling

    Sassi, R.; Marcuzzi, F.; Mazzoli, C.


    One of the main goals of metamorphic petrology is to obtain information on the variations of metamorphic P-T conditions during orogenesis (P-T-t paths). For this purpose petrologists are aware of the potentiality of studying reaction microstructures, although results are not always satisfactory as in most cases qualitative approaches, failing on the real meaning of specific microstructral relationships, are often adopted. Thus, the present research aimed to study the petrogenetic meaning of reaction microstructure in metamorphic rocks through the formulation of a new true three-dimensional finite-element model. For this purpose, different petrologically well studied metamorphic microstructural situations have been selected, in order to identify information, variables and constraints fundamental for the development of the model. A generalised finite-elements model (FEM) has been developed, applicable to any microstructural situation, independently on grain-size and distribution of minerals in the matrix, and able to also consider growth anisotropies, intracrystalline diffusion, pressure solution, and possibly anisotropy of the strain field. This model is based on a combination of the usual diffusion linear equations used in current irreversible thermodynamic models, providing constraints on absolute values of diffusion coefficients of chemical components, chemical potential gradients and time of reactions during metamorphism, starting from information on textural anisotropies observed in metamorphic rocks. In the model, parameterization is given by diffusion, convection and reaction coefficients of each chemical species within each finite element, which dimension is equal to the spatial resolution of the experimentally measured input data (i.e. SEM elemental maps). Thus, parameterization is able to describe locally heterogeneous reaction phenomena although based on a basically linear partial derivative differential model. Such a discretization of the continuum model

  15. Reaction of Topopah Spring tuff with J-13 water: a geochemical modeling approach using the EQ3/6 reaction path code

    Delany, J.M.


    EQ3/6 geochemical modeling code package was used to investigate the interaction of the Topopah Spring Tuff and J-13 water at high temperatures. EQ3/6 input parameters were obtained from the results of laboratory experiments using USW G-1 core and J-13 water. Laboratory experiments were run at 150 and 250{sup 0}C for 66 days using both wafer-size and crushed tuff. EQ3/6 modeling reproduced results of the 150{sup 0}C experiments except for a small increase in the concentration of potassium that occurs in the first few days of the experiments. At 250{sup 0}C, the EQ3/6 modeling reproduced the major water/rock reactions except for a small increase in potassium, similar to that noted above, and an overall increase in aluminum. The increase in potassium concentration cannot be explained at this time, but the increase in A1 concentration is believed to be caused by the lack of thermodynamic data in the EQ3/6 data base for dachiardite, a zeolite observed as a run product at 250{sup 0}C. The ability to reproduce the majority of the experimental rock/water interactions at 150{sup 0}C validates the use of EQ3/6 as a geochemical modeling tool that can be used to theoretically investigate physical/chemical environments in support of the Waste Package Task of NNWSI.

  16. Combining water-rock interaction experiments with reaction path and reactive transport modelling to predict reservoir rock evolution in an enhanced geothermal system

    Kuesters, Tim; Mueller, Thomas; Renner, Joerg


    Reliably predicting the evolution of mechanical and chemical properties of reservoir rocks is crucial for efficient exploitation of enhanced geothermal systems (EGS). For example, dissolution and precipitation of individual rock forming minerals often result in significant volume changes, affecting the hydraulic rock properties and chemical composition of fluid and solid phases. Reactive transport models are typically used to evaluate and predict the effect of the internal feedback of these processes. However, a quantitative evaluation of chemo-mechanical interaction in polycrystalline environments is elusive due to poorly constrained kinetic data of complex mineral reactions. In addition, experimentally derived reaction rates are generally faster than reaction rates determined from natural systems, likely a consequence of the experimental design: a) determining the rate of a single process only, e.g. the dissolution of a mineral, and b) using powdered sample materials and thus providing an unrealistically high reaction surface and at the same time eliminating the restrictions on element transport faced in-situ for fairly dense rocks. In reality, multiple reactions are coupled during the alteration of a polymineralic rocks in the presence of a fluid and the rate determining process of the overall reactions is often difficult to identify. We present results of bulk rock-water interaction experiments quantifying alteration reactions between pure water and a granodiorite sample. The rock sample was chosen for its homogenous texture, small and uniform grain size (˜0.5 mm in diameter), and absence of pre-existing alteration features. The primary minerals are plagioclase (plg - 58 vol.%), quartz (qtz - 21 vol.%), K-feldspar (Kfs - 17 vol.%), biotite (bio - 3 vol.%) and white mica (wm - 1 vol.%). Three sets of batch experiments were conducted at 200 ° C to evaluate the effect of reactive surface area and different fluid path ways using (I) powders of the bulk rock with

  17. Efficient path sampling on multiple reaction channels

    van Erp, Titus S.


    Due to the time scale problem, rare events are not accessible by straight forward molecular dynamics. The presence of multiple reaction channels complicates the problem even further. The feasibility of the standard free energy based methods relies strongly on the success in finding a proper reaction coordinate. This can be very difficult task in high-dimensional complex systems and even more if several distinct reaction channels exist. Moreover, even if a proper reaction coordinate can be fou...

  18. Business model innovation paths

    Chesbrough, H.; Di Minin, Alberto; Piccaluga, A.


    This chapter explains the business model concept and explores the reasons why “innovation” and “innovation in services” are no longer exclusively a technological issue. Rather, we highlight that business models are critical components at the centre of business innovation processes. We also attempt

  19. Reaction paths of the water-assisted neutral hydrolysis of ethyl acetate.

    Yamabe, Shinichi; Tsuchida, Noriko; Hayashida, Yousuke


    Density functional theory calculations were conducted on the title reactions with explicit inclusion of a variety of water molecules. Concerted reaction paths were examined first in the reaction model, ester(H2O)n --> MeCOOH(H2O)(n-1)EtOH, with n = 1-4. Their Gibbs activation energies are much larger than the experimental value, and the concerted paths are unfavorable. Various stepwise paths were investigated, and the ester(H2O)4 reactant gives a likely stepwise path. The n = 4 based reaction models, n = 4 + 5 and n = 4 + 12, were found to have similar proton-relay shapes with good hydrogen-bond directionality. The distinction of either the concerted or the stepwise path is described by the position of only one proton in the "junction" water molecule.

  20. The thermodynamic natural path in chemical reaction kinetics

    Moishe garfinkle


    Full Text Available The Natural Path approach to chemical reaction kinetics was developed to bridge the considerable gap between the Mass Action mechanistic approach and the non-mechanistic irreversible thermodynamic approach. The Natural Path approach can correlate empirical kinetic data with a high degree precision, as least equal to that achievable by the Mass-Action rate equations, but without recourse mechanistic considerations. The reaction velocities arising from the particular rate equation chosen by kineticists to best represent the kinetic behavior of a chemical reaction are the natural outcome of the Natural Path approach. Moreover, by virtue of its thermodynamic roots, equilibrium thermodynamic functions can be extracted from reaction kinetic data with considerable accuracy. These results support the intrinsic validity of the Natural Path approach.

  1. Reaction Path Optimization with Holonomic Constraints and Kinetic Energy Potentials.

    Brokaw, Jason B; Haas, Kevin R; Chu, Jhih-Wei


    Two methods are developed to enhance the stability, efficiency, and robustness of reaction path optimization using a chain of replicas. First, distances between replicas are kept equal during path optimization via holonomic constraints. Finding a reaction path is, thus, transformed into a constrained optimization problem. This approach avoids force projections for finding minimum energy paths (MEPs), and fast-converging schemes such as quasi-Newton methods can be readily applied. Second, we define a new objective function - the total Hamiltonian - for reaction path optimization, by combining the kinetic energy potential of each replica with its potential energy function. Minimizing the total Hamiltonian of a chain determines a minimum Hamiltonian path (MHP). If the distances between replicas are kept equal and a consistent force constant is used, then the kinetic energy potentials of all replicas have the same value. The MHP in this case is the most probable isokinetic path. Our results indicate that low-temperature kinetic energy potentials (optimization and can significantly reduce the required steps of minimization by 2-3 times without causing noticeable differences between a MHP and MEP. These methods are applied to three test cases, the C7eq-to-Cax isomerization of an alanine dipeptide, the (4)C1-to-(1)C4 transition of an α-d-glucopyranose, and the helix-to-sheet transition of a GNNQQNY heptapeptide. By applying the methods developed in this work, convergence of reaction path optimization can be achieved for these complex transitions, involving full atomic details and a large number of replicas (>100). For the case of helix-to-sheet transition, we identify pathways whose energy barriers are consistent with experimental measurements. Further, we develop a method based on the work energy theorem to quantify the accuracy of reaction paths and to determine whether the atoms used to define a path are enough to provide quantitative estimation of energy barriers.

  2. Nonlinear reaction coordinate analysis in the reweighted path ensemble

    Lechner, W.; Rogal, J.; Juraszek, J.; Ensing, B.; Bolhuis, P.G.


    We present a flexible nonlinear reaction coordinate analysis method for the transition path ensemble based on the likelihood maximization approach developed by Peters and Trout [J. Chem. Phys. 125, 054108 (2006)] . By parametrizing the reaction coordinate by a string of images in a collective variab

  3. A benchmark for reaction coordinates in the transition path ensemble.

    Li, Wenjin; Ma, Ao


    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.

  4. The enzymatic reaction catalyzed by lactate dehydrogenase exhibits one dominant reaction path

    Masterson, Jean E.; Schwartz, Steven D.


    Enzymes are the most efficient chemical catalysts known, but the exact nature of chemical barrier crossing in enzymes is not fully understood. Application of transition state theory to enzymatic reactions indicates that the rates of all possible reaction paths, weighted by their relative probabilities, must be considered in order to achieve an accurate calculation of the overall rate. Previous studies in our group have shown a single mechanism for enzymatic barrier passage in human heart lactate dehydrogenase (LDH). To ensure that this result was not due to our methodology insufficiently sampling reactive phase space, we implement high-perturbation transition path sampling in both microcanonical and canonical regimes for the reaction catalyzed by human heart LDH. We find that, although multiple, distinct paths through reactive phase space are possible for this enzymatic reaction, one specific reaction path is dominant. Since the frequency of these paths in a canonical ensemble is inversely proportional to the free energy barriers separating them from other regions of phase space, we conclude that the rarer reaction paths are likely to have a negligible contribution. Furthermore, the non-dominate reaction paths correspond to altered reactive conformations and only occur after multiple steps of high perturbation, suggesting that these paths may be the result of non-biologically significant changes to the structure of the enzymatic active site.

  5. Exploring chemical reaction mechanisms through harmonic Fourier beads path optimization.

    Khavrutskii, Ilja V; Smith, Jason B; Wallqvist, Anders


    Here, we apply the harmonic Fourier beads (HFB) path optimization method to study chemical reactions involving covalent bond breaking and forming on quantum mechanical (QM) and hybrid QM∕molecular mechanical (QM∕MM) potential energy surfaces. To improve efficiency of the path optimization on such computationally demanding potentials, we combined HFB with conjugate gradient (CG) optimization. The combined CG-HFB method was used to study two biologically relevant reactions, namely, L- to D-alanine amino acid inversion and alcohol acylation by amides. The optimized paths revealed several unexpected reaction steps in the gas phase. For example, on the B3LYP∕6-31G(d,p) potential, we found that alanine inversion proceeded via previously unknown intermediates, 2-iminopropane-1,1-diol and 3-amino-3-methyloxiran-2-ol. The CG-HFB method accurately located transition states, aiding in the interpretation of complex reaction mechanisms. Thus, on the B3LYP∕6-31G(d,p) potential, the gas phase activation barriers for the inversion and acylation reactions were 50.5 and 39.9 kcal∕mol, respectively. These barriers determine the spontaneous loss of amino acid chirality and cleavage of peptide bonds in proteins. We conclude that the combined CG-HFB method further advances QM and QM∕MM studies of reaction mechanisms.

  6. Path modeling and process control

    Høskuldsson, Agnar; Rodionova, O.; Pomerantsev, A.


    and having three or more stages. The methods are applied to a process control of a multi-stage production process having 25 variables and one output variable. When moving along the process, variables change their roles. It is shown how the methods of path modeling can be applied to estimate variables...... of the next stage with the purpose of obtaining optimal or almost optimal quality of the output variable. An important aspect of the methods presented is the possibility of extensive graphic analysis of data that can provide the engineer with a detailed view of the multi-variate variation in data.......Many production processes are carried out in stages. At the end of each stage, the production engineer can analyze the intermediate results and correct process parameters (variables) of the next stage. Both analysis of the process and correction to process parameters at next stage should...

  7. State Space Path Integrals for Electronically Nonadiabatic Reaction Rates

    Duke, Jessica Ryan


    We present a state-space-based path integral method to calculate the rate of electron transfer (ET) in multi-state, multi-electron condensed-phase processes. We employ an exact path integral in discrete electronic states and continuous Cartesian nuclear variables to obtain a transition state theory (TST) estimate to the rate. A dynamic recrossing correction to the TST rate is then obtained from real-time dynamics simulations using mean field ring polymer molecular dynamics. We employ two different reaction coordinates in our simulations and show that, despite the use of mean field dynamics, the use of an accurate dividing surface to compute TST rates allows us to achieve remarkable agreement with Fermi's golden rule rates for nonadiabatic ET in the normal regime of Marcus theory. Further, we show that using a reaction coordinate based on electronic state populations allows us to capture the turnover in rates for ET in the Marcus inverted regime.

  8. Reaction paths of the water-assisted solvolysis of N,N-dimethylformamide.

    Tsuchida, Noriko; Satou, Harumi; Yamabe, Shinichi


    Density functional theory calculations were conducted on the title reactions with explicit inclusion of a variety of water molecules, H-CO-NMe2+MeOH+(H2O)n-->H-CO-OMe+HNMe2+(H2O)n. Geometries of transition states, reactant-like complexes and product-like ones were determined by the use of RB3LYP/6-31G(d) SCRF=dipole. Concerted paths were examined with n=0-3. Their Gibbs activation energies are larger than the experimental value. Stepwise paths were also investigated with n=2-4. The n=4 model has the energy close to the experimental value. However, when the catalytic water molecules were added to the n=4 one, the stepwise path was switched to the concerted one. A systematic comparison of the concerted path with n=2+1, 2+2, 2+3, 2+4, 2+5, 2+4+4, and 2+5+5 models was made, and the water-dimer based reaction path was found to be most favorable. The contrast between the concerted path of the amide solvolysis (and hydrolysis) and the stepwise one of the ester hydrolysis was discussed in terms of the frontier-orbital theory.

  9. Multi-block and path modelling procedures

    Høskuldsson, Agnar


    The author has developed a unified theory of path and multi-block modelling of data. The data blocks are arranged in a directional path. Each data block can lead to one or more data blocks. It is assumed that there is given a collection of input data blocks. Each of them is supposed to describe one...

  10. Consistent Partial Least Squares Path Modeling

    Dijkstra, Theo K.; Henseler, Jörg


    This paper resumes the discussion in information systems research on the use of partial least squares (PLS) path modeling and shows that the inconsistency of PLS path coefficient estimates in the case of reflective measurement can have adverse consequences for hypothesis testing. To remedy this, the

  11. Inverse Geochemical Reaction Path Modelling and the Impact of Climate Change on Hydrologic Structure in Snowmelt-Dominated Catchments in the Southwestern USA

    Driscoll, J. M.; Meixner, T.; Molotch, N. P.; Sickman, J. O.; Williams, M. W.; McIntosh, J. C.; Brooks, P. D.


    Snowmelt from alpine catchments provides 70-80% of the American Southwest's water resources. Climate change threatens to alter the timing and duration of snowmelt in high elevation catchments, which may also impact the quantity and the quality of these water resources. Modelling of these systems provides a robust theoretical framework to process the information extracted from the sparse physical measurement available in these sites due to their remote locations. Mass-balance inverse geochemical models (via PHREEQC, developed by the USGS) were applied to two snowmelt-dominated catchments; Green Lake 4 (GL4) in the Rockies and Emerald Lake (EMD) in the Sierra Nevada. Both catchments primarily consist of granite and granodiorite with a similar bulk geochemistry. The inputs for the models were the initial (snowpack) and final (catchment output) hydrochemistry and a catchment-specific suite of mineral weathering reactions. Models were run for wet and dry snow years, for early and late time periods (defined hydrologically as 1/2 of the total volume for the year). Multiple model solutions were reduced to a representative suite of reactions by choosing the model solution with the fewest phases and least overall phase change. The dominant weathering reactions (those which contributed the most solutes) were plagioclase for GL4 and albite for EMD. Results for GL4 show overall more plagioclase weathering during the dry year (214.2g) than wet year (89.9g). Both wet and dry years show more weathering in the early time periods (63% and 56%, respectively). These results show that the snowpack and outlet are chemically more similar during wet years than dry years. A possible hypothesis to explain this difference is a change in contribution from subsurface storage; during the wet year the saturated catchment reduces contact with surface materials that would result in mineral weathering reactions by some combination of reduced infiltration and decreased subsurface transit time. By

  12. Path optimization by a variational reaction coordinate method. I. Development of formalism and algorithms.

    Birkholz, Adam B; Schlegel, H Bernhard


    The development of algorithms to optimize reaction pathways between reactants and products is an active area of study. Existing algorithms typically describe the path as a discrete series of images (chain of states) which are moved downhill toward the path, using various reparameterization schemes, constraints, or fictitious forces to maintain a uniform description of the reaction path. The Variational Reaction Coordinate (VRC) method is a novel approach that finds the reaction path by minimizing the variational reaction energy (VRE) of Quapp and Bofill. The VRE is the line integral of the gradient norm along a path between reactants and products and minimization of VRE has been shown to yield the steepest descent reaction path. In the VRC method, we represent the reaction path by a linear expansion in a set of continuous basis functions and find the optimized path by minimizing the VRE with respect to the linear expansion coefficients. Improved convergence is obtained by applying constraints to the spacing of the basis functions and coupling the minimization of the VRE to the minimization of one or more points along the path that correspond to intermediates and transition states. The VRC method is demonstrated by optimizing the reaction path for the Müller-Brown surface and by finding a reaction path passing through 5 transition states and 4 intermediates for a 10 atom Lennard-Jones cluster.

  13. Unified path integral approach to theories of diffusion-influenced reactions

    Prüstel, Thorsten; Meier-Schellersheim, Martin


    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.

  14. The Lost City hydrothermal system: Constraints imposed by vent fluid chemistry and reaction path models on subseafloor heat and mass transfer processes

    Seyfried, W. E.; Pester, Nicholas J.; Tutolo, Benjamin M.; Ding, Kang


    Since the first reported discovery of the Lost City hydrothermal system in 2001, it was recognized that seawater alteration of ultramafic rocks plays a key role in the composition of the coexisting vent fluids. The unusually high pH and high concentrations of H2 and CH4 provide compelling evidence for this. Here we report the chemistry of hydrothermal fluids sampled from two vent structures (Beehive: ∼90-116 °C, and M6: ∼75 °C) at Lost City in 2008 during cruise KNOX18RR using ROV Jason 2 and R/V Revelle assets. The vent fluid chemistry at both sites reveals considerable overlap in concentrations of dissolved gases (H2, CH4), trace elements (Cs, Rb, Li, B and Sr), and major elements (SO4, Ca, K, Na, Cl), including a surprising decrease in dissolved Cl, suggesting a common source fluid is feeding both sites. The absence of Mg and relatively high concentrations of Ca and sulfate suggest solubility control by serpentine-diopside-anhydrite, while trace alkali concentrations, especially Rb and Cs, are high, assuming a depleted mantle protolith. In both cases, but especially for Beehive vent fluid, the silica concentrations are well in excess of those expected for peridotite alteration and the coexistence of serpentine-brucite at all reasonable temperatures. However, both the measured pH and silica values are in better agreement with serpentine-diopside-tremolite-equilibria. Geochemical modeling demonstrates that reaction of plagioclase with serpentinized peridotite can shift the chemical system away from brucite and into the tremolite stability field. This is consistent with the complex intermingling of peridotite and gabbroic bodies commonly observed within the Atlantis Massif. We speculate the existence of such plagioclase bearing peridotite may also account for the highly enriched trace alkali (Cs, Rb) concentrations in the Lost City vent fluids. Additionally, reactive transport modeling taking explicit account of temperature dependent rates of mineral

  15. Modeling DNA Dynamics by Path Integrals

    Zoli, Marco


    Complementary strands in DNA double helix show temporary fluctuational openings which are essential to biological functions such as transcription and replication of the genetic information. Such large amplitude fluctuations, known as the breathing of DNA, are generally localized and, microscopically, are due to the breaking of the hydrogen bonds linking the base pairs (\\emph{bps}). I apply imaginary time path integral techniques to a mesoscopic Hamiltonian which accounts for the helicoidal geometry of a short circular DNA molecule. The \\emph{bps} displacements with respect to the ground state are interpreted as time dependent paths whose amplitudes are consistent with the model potential for the hydrogen bonds. The portion of the paths configuration space contributing to the partition function is determined by selecting the ensemble of paths which fulfill the second law of thermodynamics. Computations of the thermodynamics in the denaturation range show the energetic advantage for the equilibrium helicoidal g...

  16. PP: A graphics post-processor for the EQ6 reaction path code

    Stockman, H.W.


    The PP code is a graphics post-processor and plotting program for EQ6, a popular reaction-path code. PP runs on personal computers, allocates memory dynamically, and can handle very large reaction path runs. Plots of simple variable groups, such as fluid and solid phase composition, can be obtained with as few as two keystrokes. Navigation through the list of reaction path variables is simple and efficient. Graphics files can be exported for inclusion in word processing documents and spreadsheets, and experimental data may be imported and superposed on the reaction path runs. The EQ6 thermodynamic database can be searched from within PP, to simplify interpretation of complex plots.

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

    Tervo, Christopher J; Reed, Jennifer L


    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.

  18. Predictors of Retirement Satisfaction: A Path Model.

    Kremer, Yael


    Examined adjustment to retirement among 310 former industrial and service workers. Respondents had come to terms with retirement and enjoyed their more relaxed lifestyle. Dominant variables in the path model were retirees' satisfaction with specific aspects of retirement: giving up work, activities with family and friends, rest, and free time. (BH)

  19. Thermochemistry, reaction paths, and kinetics on the tert-isooctane radical reaction with O2.

    Snitsiriwat, Suarwee; Bozzelli, Joseph W


    Thermochemical properties of tert-isooctane hydroperoxide and its radicals are determined by computational chemistry. Enthalpies are determined using isodesmic reactions with B3LYP density function and CBS QB3 methods. Application of group additivity with comparison to calculated values is illustrated. Entropy and heat capacities are determined using geometric parameters and frequencies from the B3LYP/6-31G(d,p) calculations for the lowest energy conformer. Internal rotor potentials are determined for the tert-isooctane hydroperoxide and its radicals in order to identify isomer energies. Recommended values derived from the most stable conformers of tert-isooctane hydroperoxide of are -77.85 ± 0.44 kcal mol(-1). Isooctane is a highly branched molecule, and its structure has a significant effect on its thermochemistry and reaction barriers. Intramolecular interactions are shown to have a significant effect on the enthalpy of the isooctane parent and its radicals on peroxy/peroxide systems, the R• + O2 well depths and unimolecular reaction barriers. Bond dissociation energies and well depths, for tert-isooctane hydroperoxide → R• + O2 are 33.5 kcal mol(-1) compared to values of ∼38 to 40 kcal mol(-1) for the smaller tert-butyl-O2 → R• + O2. Transition states and kinetic parameters for intramolecular hydrogen atom transfer and molecular elimination channels are characterized to evaluate reaction paths and kinetics. Kinetic parameters are determined versus pressure and temperature for the chemically activated formation and unimolecular dissociation of the peroxide adducts. Multifrequency quantum RRK (QRRK) analysis is used for k(E) with master equation analysis for falloff. The major reaction paths at 1000 K are formation of isooctane plus HO2 followed by cyclic ether plus OH. Stabilization of the tert-isooctane hydroperoxy radical becomes important at lower temperatures.

  20. Path Models of Vocal Emotion Communication.

    Tanja Bänziger

    Full Text Available We propose to use a comprehensive path model of vocal emotion communication, encompassing encoding, transmission, and decoding processes, to empirically model data sets on emotion expression and recognition. The utility of the approach is demonstrated for two data sets from two different cultures and languages, based on corpora of vocal emotion enactment by professional actors and emotion inference by naïve listeners. Lens model equations, hierarchical regression, and multivariate path analysis are used to compare the relative contributions of objectively measured acoustic cues in the enacted expressions and subjective voice cues as perceived by listeners to the variance in emotion inference from vocal expressions for four emotion families (fear, anger, happiness, and sadness. While the results confirm the central role of arousal in vocal emotion communication, the utility of applying an extended path modeling framework is demonstrated by the identification of unique combinations of distal cues and proximal percepts carrying information about specific emotion families, independent of arousal. The statistical models generated show that more sophisticated acoustic parameters need to be developed to explain the distal underpinnings of subjective voice quality percepts that account for much of the variance in emotion inference, in particular voice instability and roughness. The general approach advocated here, as well as the specific results, open up new research strategies for work in psychology (specifically emotion and social perception research and engineering and computer science (specifically research and development in the domain of affective computing, particularly on automatic emotion detection and synthetic emotion expression in avatars.

  1. Path Models of Vocal Emotion Communication.

    Bänziger, Tanja; Hosoya, Georg; Scherer, Klaus R


    We propose to use a comprehensive path model of vocal emotion communication, encompassing encoding, transmission, and decoding processes, to empirically model data sets on emotion expression and recognition. The utility of the approach is demonstrated for two data sets from two different cultures and languages, based on corpora of vocal emotion enactment by professional actors and emotion inference by naïve listeners. Lens model equations, hierarchical regression, and multivariate path analysis are used to compare the relative contributions of objectively measured acoustic cues in the enacted expressions and subjective voice cues as perceived by listeners to the variance in emotion inference from vocal expressions for four emotion families (fear, anger, happiness, and sadness). While the results confirm the central role of arousal in vocal emotion communication, the utility of applying an extended path modeling framework is demonstrated by the identification of unique combinations of distal cues and proximal percepts carrying information about specific emotion families, independent of arousal. The statistical models generated show that more sophisticated acoustic parameters need to be developed to explain the distal underpinnings of subjective voice quality percepts that account for much of the variance in emotion inference, in particular voice instability and roughness. The general approach advocated here, as well as the specific results, open up new research strategies for work in psychology (specifically emotion and social perception research) and engineering and computer science (specifically research and development in the domain of affective computing, particularly on automatic emotion detection and synthetic emotion expression in avatars).

  2. Mixed quantum-classical reaction path dynamics of C2H5F --> C2H4 + HF.

    Stopera, Christopher J; Bladow, Landon L; Thweatt, W David; Page, Michael


    A mixed quantum-classical method for calculating product energy partitioning based on a reaction path Hamiltonian is presented and applied to HF elimination from fluoroethane. The goal is to describe the effect of the potential energy release on the product energies using a simple model of quantized transverse vibrational modes coupled to a classical reaction path via the path curvature. Calculations of the minimum energy path were done at the B3LYP/6-311++G(2d,2p) and MP2/6-311++G** levels of theory, followed by energy-partitioning dynamics calculations. The results for the final HF vibrational state distribution were found to be in good qualitative agreement with both experimental studies and quasiclassical trajectory simulations.

  3. Joint modeling of constrained path enumeration and path choice behavior: a semi-compensatory approach

    Kaplan, Sigal; Prato, Carlo Giacomo


    A behavioural and a modelling framework are proposed for representing route choice from a path set that satisfies travellers’ spatiotemporal constraints. Within the proposed framework, travellers’ master sets are constructed by path generation, consideration sets are delimited according to spatio...... constraints are related to travellers’ socio-economic characteristics and that path choice is related to minimizing time and avoiding congestion....

  4. Automated Prediction of Catalytic Mechanism and Rate Law Using Graph-Based Reaction Path Sampling.

    Habershon, Scott


    In a recent article [ J. Chem. Phys. 2015 , 143 , 094106 ], we introduced a novel graph-based sampling scheme which can be used to generate chemical reaction paths in many-atom systems in an efficient and highly automated manner. The main goal of this work is to demonstrate how this approach, when combined with direct kinetic modeling, can be used to determine the mechanism and phenomenological rate law of a complex catalytic cycle, namely cobalt-catalyzed hydroformylation of ethene. Our graph-based sampling scheme generates 31 unique chemical products and 32 unique chemical reaction pathways; these sampled structures and reaction paths enable automated construction of a kinetic network model of the catalytic system when combined with density functional theory (DFT) calculations of free energies and resultant transition-state theory rate constants. Direct simulations of this kinetic network across a range of initial reactant concentrations enables determination of both the reaction mechanism and the associated rate law in an automated fashion, without the need for either presupposing a mechanism or making steady-state approximations in kinetic analysis. Most importantly, we find that the reaction mechanism which emerges from these simulations is exactly that originally proposed by Heck and Breslow; furthermore, the simulated rate law is also consistent with previous experimental and computational studies, exhibiting a complex dependence on carbon monoxide pressure. While the inherent errors of using DFT simulations to model chemical reactivity limit the quantitative accuracy of our calculated rates, this work confirms that our automated simulation strategy enables direct analysis of catalytic mechanisms from first principles.

  5. Coupling sample paths to the partial thermodynamic limit in stochastic chemical reaction networks

    Levien, Ethan


    We present a new technique for reducing the variance in Monte Carlo estimators of stochastic chemical reaction networks. Our method makes use of the fact that many stochastic reaction networks converge to piecewise deterministic Markov processes in the large system-size limit. The statistics of the piecewise deterministic process can be obtained much more efficiently than those of the exact process. By coupling sample paths of the exact model to the piecewise deterministic process we are able to reduce the variance, and hence the computational complexity of the Monte Carlo estimator. In addition to rigorous results concerning the asymptotic behavior of our method, numerical simulations are performed on some simple biological models suggesting that significant computational gains are made for even moderate system-sizes.

  6. Kinetic modeling of reactions in Foods

    Boekel, van M.A.J.S.


    The level of quality that food maintains as it travels down the production-to-consumption path is largely determined by the chemical, biochemical, physical, and microbiological changes that take place during its processing and storage. Kinetic Modeling of Reactions in Foods demonstrates how to effec

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

    Aono, Masashi; Wakabayashi, Masamitsu


    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 [ ]. 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.

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

    Aono, Masashi; Wakabayashi, Masamitsu


    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 []. 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.

  9. A Networks Approach to Modeling Enzymatic Reactions.

    Imhof, P


    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.

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

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


    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

  11. Topological studies on IRC paths of the isomerization reaction of silicon methyl- nitrene

    石彦波; 郑世钧; 孟令鹏


    On the basis of kinetic study of isomerization reaction of H3Si-N, ab initio (RHF, UHF/6-31G) calculations on some points of the singlet and triplet reaction paths were carried out. The breakage and formation of chemical bond in the reaction are discussed. The calculated results show that there is a transitional structure of three-membered ring on each of reaction paths. A ’structural transition region’ and a ’structural transition state’ in both of studied reaction are found. Our previous conclusion that the structure transition state (STS) always appears before the energy transition state (ETS) in endothermic reaction and after ETS in exothermic reaction is further confirmed. The relationship between the change of spin density distribution and the structural transition state are investigated.

  12. Rare events via multiple reaction channels sampled by path replica exchange

    Bolhuis, P.G.


    Transition path sampling (TPS) was developed for studying activated processes in complex systems with unknown reaction coordinate. Transition interface sampling (TIS) allows efficient evaluation of the rate constants. However, when the transition can occur via more than one reaction channel separate

  13. DFT study on adduct reaction paths of GaN MOCVD growth

    SHI; JunCao; ZUO; Ran; MENG; SuCi


    The adduct reaction paths for GaN growth by metal organic chemical vapor deposition (MOCVD) were studied by quantum chemical calculations employing density functional theory (DFT). Five possible adduct reaction paths with or without the ex-cess NH3were proposed and the corresponding potential energy surfaces were calculated. From the calculation results, it is concluded that after the formation of DMGNH2from TMG:NH3, the further decomposition paths have very slim probability because of the high energy barriers; whereas the oligomerization pathway to form oligomers [DMGNH2]x(x=2, 3) is probable,because of zero energy barrier. Since the oligomers tend to further polymerize, the nanoparticles are easily formed through this path. When NH3is in excess, TMG:NH3 tends to combine with the second NH3to form two new complexes: the coordination-bonded compound H3N:TMG:NH3and the hydrogen-bonded compound TMG:NH3 NH3. The formation of hydrogen-bonded compound TMG:NH3 NH3 will be more probable because of the lower energy than H3N:TMG:NH3. By comparing the potential energy surfaces in five adduct reaction paths, we postulate that, under the growth conditions of GaN MOCVD, the formation of hydrogen-bonded compound TMG:NH3 NH3 followed by the reversible decomposition may be the main reaction path for GaN thin film growth; while the adduct oligomerization path to generate oligomers [DMGNH2]2 and [DMGNH2]3might be the main reaction path for nanoparticles formation.

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

    Zheng, Jingjing; Truhlar, Donald G


    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.

  15. Structural equation models from paths to networks

    Westland, J Christopher


    This compact reference surveys the full range of available structural equation modeling (SEM) methodologies.  It reviews applications in a broad range of disciplines, particularly in the social sciences where many key concepts are not directly observable.  This is the first book to present SEM’s development in its proper historical context–essential to understanding the application, strengths and weaknesses of each particular method.  This book also surveys the emerging path and network approaches that complement and enhance SEM, and that will grow in importance in the near future.  SEM’s ability to accommodate unobservable theory constructs through latent variables is of significant importance to social scientists.  Latent variable theory and application are comprehensively explained, and methods are presented for extending their power, including guidelines for data preparation, sample size calculation, and the special treatment of Likert scale data.  Tables of software, methodologies and fit st...

  16. NUCLEAR PHYSICS: Probing the Dissipation Mechanism in Ternary Reactions of 197Au+197Au by Mean Free Path of Nucleons

    Tian, Jun-Long; Li, Xian; Yan, Shi-Wei; Wu, Xi-Zhen; Li, Zhu-Xia


    the collision of very heavy nuclei 197Au+197Au at 15 A MeV has been studied within the improved quantum molecular dynamics model. A class of ternary events satisfying nearly complete balance of mass numbers is selected. The experimental mass distributions for the system 197Au+197Au ternary fission fragments, the heaviest (A1), the intermediate (A2) and the lightest (A3), are reproduced well. The mean free path of nucleons in the reaction system is studied and the shorter mean free path is responsible for the ternary fission with three mass comparable fragments, in which the two-body dissipation mechanism plays a dominant role.

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

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


    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.

  18. Reaction paths of phosphine dissociation on silicon (001)

    Warschkow, O.; Curson, N. J.; Schofield, S. R.; Marks, N. A.; Wilson, H. F.; Radny, M. W.; Smith, P. V.; Reusch, T. C. G.; McKenzie, D. R.; Simmons, M. Y.


    Using density functional theory and guided by extensive scanning tunneling microscopy (STM) image data, we formulate a detailed mechanism for the dissociation of phosphine (PH3) molecules on the Si(001) surface at room temperature. We distinguish between a main sequence of dissociation that involves PH2+H, PH+2H, and P+3H as observable intermediates, and a secondary sequence that gives rise to PH+H, P+2H, and isolated phosphorus adatoms. The latter sequence arises because PH2 fragments are surprisingly mobile on Si(001) and can diffuse away from the third hydrogen atom that makes up the PH3 stoichiometry. Our calculated activation energies describe the competition between diffusion and dissociation pathways and hence provide a comprehensive model for the numerous adsorbate species observed in STM experiments.

  19. Reaction paths of phosphine dissociation on silicon (001)

    Warschkow, O.; McKenzie, D. R. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of Sydney, Sydney, NSW 2006 (Australia); Curson, N. J. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of New South Wales, Sydney, NSW 2052 (Australia); London Centre for Nanotechnology and Department of Electronic and Electrical Engineering, University College London, 17-19 Gordon Street, London WC1H 0AH (United Kingdom); Schofield, S. R. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of New South Wales, Sydney, NSW 2052 (Australia); London Centre for Nanotechnology and Department of Physics and Astronomy, University College, 17-19 Gordon Street, London WC1H 0AH (United Kingdom); Marks, N. A. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of Sydney, Sydney, NSW 2006 (Australia); Discipline of Physics & Astronomy, Curtin University, GPO Box U1987, Perth, WA (Australia); Wilson, H. F. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of Sydney, Sydney, NSW 2006 (Australia); CSIRO Virtual Nanoscience Laboratory, Parkville, VIC 3052 (Australia); School of Applied Sciences, RMIT University, Melbourne, VIC 3000 (Australia); Radny, M. W.; Smith, P. V. [School of Mathematical and Physical Sciences, The University of Newcastle, Callaghan, NSW 2308 (Australia); Reusch, T. C. G.; Simmons, M. Y. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of New South Wales, Sydney, NSW 2052 (Australia)


    Using density functional theory and guided by extensive scanning tunneling microscopy (STM) image data, we formulate a detailed mechanism for the dissociation of phosphine (PH{sub 3}) molecules on the Si(001) surface at room temperature. We distinguish between a main sequence of dissociation that involves PH{sub 2}+H, PH+2H, and P+3H as observable intermediates, and a secondary sequence that gives rise to PH+H, P+2H, and isolated phosphorus adatoms. The latter sequence arises because PH{sub 2} fragments are surprisingly mobile on Si(001) and can diffuse away from the third hydrogen atom that makes up the PH{sub 3} stoichiometry. Our calculated activation energies describe the competition between diffusion and dissociation pathways and hence provide a comprehensive model for the numerous adsorbate species observed in STM experiments.

  20. Searching for the minimum energy path in the sulfuryl transfer reaction catalyzed by human estrogen sulfotransferase: Role of enzyme dynamics

    Lin, Ping; Yang, Weitao; Pedersen, Lars C.; Negishi, Masa; Pedersen, Lee G.

    The enzymatic transfer of a sulfuryl group from the ubiquitous biological source of sulfate 3?-phosphoadenosine 5?-phosphosulfate (PAPS) to estrogen is investigated by the pseudo-bond quantum mechanical/molecular mechanical method (QM/MM) method. Calculations of the reaction path are performed starting with models based on two crystal structures, which differ in information about the cofactor and substrates. In addition, a subsequent relaxation of the enzyme was performed with the found transition state frozen, followed by redetermination of the path. An activation barrier of 22 kcal/mol is estimated. The reaction mechanism features a proton transfer from the estrogen to a catalytic histidine followed by the rate determining SO3 transfer. The mechanism found is largely dissociative.

  1. Performance analysis of FXLMS algorithm with secondary path modeling error

    SUN Xu; CHEN Duanshi


    Performance analysis of filtered-X LMS (FXLMS) algorithm with secondary path modeling error is carried out in both time and frequency domain. It is shown firstly that the effects of secondary path modeling error on the performance of FXLMS algorithm are determined by the distribution of the relative error of secondary path model along with frequency.In case of that the distribution of relative error is uniform the modeling error of secondary path will have no effects on the performance of the algorithm. In addition, a limitation property of FXLMS algorithm is proved, which implies that the negative effects of secondary path modeling error can be compensated by increasing the adaptive filter length. At last, some insights into the "spillover" phenomenon of FXLMS algorithm are given.

  2. A Path-Analytic Model of Career Indecision.

    Hartman, Bruce W.; And Others


    Tested a path model reflecting developmental and chronic types of career indecision on counseling students (N=164) and high school students (N=155). Data from both samples supported the model, confirming the role of trait anxiety in career indecision. (JAC)

  3. Self-consistent collective coordinate for reaction path and inertial mass

    Wen, Kai


    We propose a numerical method to determine the optimal collective reaction path for the nucleus-nucleus collision, based on the adiabatic self-consistent collective coordinate (ASCC) method. We use an iterative method combining the imaginary-time evolution and the finite amplitude method, for the solution of the ASCC coupled equations. It is applied to the simplest case, the $\\alpha-\\alpha$ scattering. We determine the collective path, the potential, and the inertial mass. The results are compared with other methods, such as the constrained Hartree-Fock method, the Inglis's cranking formula, and the adiabatic time-dependent Hartree-Fock (ATDHF) method.

  4. Dynamic path bifurcation in the Beckmann reaction: support from kinetic analyses.

    Yamamoto, Yutaro; Hasegawa, Hiroto; Yamataka, Hiroshi


    The reactions of oximes to amides, known as the Beckmann rearrangement, may undergo fragmentation to form carbocations + nitriles when the migrating groups have reasonable stability as cations. The reactions of oxime sulfonates of 1-substituted-phenyl-2-propanone derivatives (7-X) and related substrates (8-X, 9a-X) in aqueous CH(3)CN gave both rearrangement products (amides) and fragmentation products (alcohols), the ratio of which depends on the system; the reactions of 7-X gave amides predominantly, whereas 9a-X yielded alcohols as the major product. The logk-logk plots between the systems gave excellent linear correlations with slopes of near unity. The results support the occurrence of path bifurcation after the rate-determining TS of the Beckmann rearrangement/fragmentation reaction, which has previously been proposed on the basis of molecular dynamics simulations. It was concluded that path-bifurcation phenomenon could be more common than thought and that a reactivity-selectivity argument based on the traditional TS theory may not always be applicable even to a well-known textbook organic reaction.

  5. Transition Path Sampling Study of the Reaction Catalyzed by Purine Nucleoside Phosphorylase

    Saen-oon, Suwipa; Schramm, Vern L.; Schwartz, Steven D.


    The Transition Path Sampling (TPS) method is a powerful technique for studying rare events in complex systems, that allows description of reactive events in atomic detail without prior knowledge of reaction coordinates and transition states. We have applied TPS in combination with a hybrid Quantum Mechanical/Molecular Mechanical (QM/MM) method to study the enzyme human purine nucleoside phosphorylase (hPNP). This enzyme catalyzes the reversible phosphorolysis of 6-oxypurine (deoxy)nucleosides to generate the corresponding purine base and (deoxy)ribose 1-phosphate. Hundreds of reactive trajectories were generated. Analysis of this transition path ensembles provides insight into the detailed mechanistic dynamics of reaction in the enzyme. Our studies have indicated a reaction mechanism involving the cleavage of the N-ribosidic bond to form transition states with substantial ribooxacarbenium ion character, that is then followed by conformational changes in the enzyme and the ribosyl group leading to migration of the anomeric carbon of the ribosyl group toward phosphate to form the product ribose 1-phosphate. This latter process is crucial in PNP, because several strong H-bonds form between active site residues in order to capture and align the phosphate nucleophile. Calculations of the commitment probability along reactive paths demonstrated the presence of a broad energy barrier at the transition state. Analysis of these transition state structures showed that bond-breaking and bond-forming distances are not a good choice for the reaction coordinate, but that the pseudorotational phase of the ribose ring is also a significant variable. PMID:20664707

  6. An Access Path Model for Physical Database Design.


    target system. 4.1 Algebraic Structure for Physical Design For the purposes of implementation-oriented design, we shall use the logical access paths...subsection, we present an algorithm for gen- erating a maximal labelling that specifies superior support for the access paths most heavily travelled. Assume...A.C.M. SIGMOD Conf., (May 79). [CARD731 Cardenas , A. F., "Evaluation and Selection of File Organization - A Model and a System," Comm. A.C.M., V 16, N

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

    Walch, Stephen P.; Taylor, Peter R.


    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.

  8. Sensory feedback in a bump attractor model of path integration.

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


    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.

  9. Influence of Solvent on Reaction Path to Synthesis of Methyl N-Phenyl Carbamate from Aniline, CO2 and Methanol

    安华良; 张丽丽; 苑保国; 赵新强; 王延吉


    Methyl N-phenyl carbamate (MPC), an important organic chemical, can be synthesized from aniline, CO2 and methanol. Catalyst Cu-Fe/ZrO2-SiO2 was first prepared and its catalytic performance for MPC synthesis was evaluated. Then the influence of solvent on the reaction path of MPC synthesis was investigated. It is found that the reaction intermediate is different with acetonitrile or methanol as a solvent. With acetonitrile as a solvent, the synthesis of MPC follows the reaction path with diphenyl urea as the intermediate, while with methanol as a solvent the reaction occurs via the reaction path with dimethyl carbonate as the intermediate. The catalytic mecha-nism of cooperative catalysis comprising metal sites, Lewis acid sites and Lewis base sites is proposed according to different reaction intermediates.

  10. Threat Modeling-Oriented Attack Path Evaluating Algorithm

    LI Xiaohong; LIU Ran; FENG Zhiyong; HE Ke


    In order to evaluate all attack paths in a threat tree,based on threat modeling theory,a weight distribution algorithm of the root node in a threat tree is designed,which computes threat coefficients of leaf nodes in two ways including threat occurring possibility and the degree of damage.Besides,an algorithm of searching attack path was also obtained in accordence with its definition.Finally,an attack path evaluation system was implemented which can output the threat coefficients of the leaf nodes in a target threat tree,the weight distribution information,and the attack paths.An example threat tree is given to verify the effectiveness of the algorithms.

  11. Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems

    Glynn, P.D.; Reardon, E.J.; Plummer, L.N.; Busenberg, E.


    Equations are presented describing equilibrium in binary solid-solution aqueous-solution (SSAS) systems after a dissolution, precipitation, or recrystallization process, as a function of the composition and relative proportion of the initial phases. Equilibrium phase diagrams incorporating the concept of stoichiometric saturation are used to interpret possible reaction paths and to demonstrate relations between stoichiometric saturation, primary saturation, and thermodynamic equilibrium states. The concept of stoichiometric saturation is found useful in interpreting and putting limits on dissolution pathways, but there currently is no basis for possible application of this concept to the prediction and/ or understanding of precipitation processes. Previously published dissolution experiments for (Ba, Sr)SO4 and (Sr, Ca)C??O3orth. solids are interpreted using equilibrium phase diagrams. These studies show that stoichiometric saturation can control, or at least influence, initial congruent dissolution pathways. The results for (Sr, Ca)CO3orth. solids reveal that stoichiometric saturation can also control the initial stages of incongruent dissolution, despite the intrinsic instability of some of the initial solids. In contrast, recrystallisation experiments in the highly soluble KCl-KBr-H2O system demonstrate equilibrium. The excess free energy of mixing calculated for K(Cl, Br) solids is closely modeled by the relation GE = ??KBr??KClRT[a0 + a1(2??KBr-1)], where a0 is 1.40 ?? 0.02, a1, is -0.08 ?? 0.03 at 25??C, and ??KBr and ??KCl are the mole fractions of KBr and KCl in the solids. The phase diagram constructed using this fit reveals an alyotropic maximum located at ??KBr = 0.676 and at a total solubility product, ???? = [K+]([Cl-] + [Br-]) = 15.35. ?? 1990.

  12. Reduction of chemical reaction models

    Frenklach, Michael


    An attempt is made to reconcile the different terminologies pertaining to reduction of chemical reaction models. The approaches considered include global modeling, response modeling, detailed reduction, chemical lumping, and statistical lumping. The advantages and drawbacks of each of these methods are pointed out.

  13. Outdoor-indoor Space: Unified Modeling and Shortest Path Search

    Jensen, Søren Kejser; Nielsen, Jens Thomas Vejlby; Lu, Hua;


    Graph models are widely used for representing the topology of outdoor space (O-Space) and indoor space (I-Space). However, existing models neglect the intersection between O-Space and I-Space, only allowing for computations such as shortest path and nearest neighbor queries in either O-Space or I...

  14. Path optimization by a variational reaction coordinate method. II. Improved computational efficiency through internal coordinates and surface interpolation.

    Birkholz, Adam B; Schlegel, H Bernhard


    Reaction path optimization is being used more frequently as an alternative to the standard practice of locating a transition state and following the path downhill. The Variational Reaction Coordinate (VRC) method was proposed as an alternative to chain-of-states methods like nudged elastic band and string method. The VRC method represents the path using a linear expansion of continuous basis functions, allowing the path to be optimized variationally by updating the expansion coefficients to minimize the line integral of the potential energy gradient norm, referred to as the Variational Reaction Energy (VRE) of the path. When constraints are used to control the spacing of basis functions and to couple the minimization of the VRE with the optimization of one or more individual points along the path (representing transition states and intermediates), an approximate path as well as the converged geometries of transition states and intermediates along the path are determined in only a few iterations. This algorithmic efficiency comes at a high per-iteration cost due to numerical integration of the VRE derivatives. In the present work, methods for incorporating redundant internal coordinates and potential energy surface interpolation into the VRC method are described. With these methods, the per-iteration cost, in terms of the number of potential energy surface evaluations, of the VRC method is reduced while the high algorithmic efficiency is maintained.

  15. Reconciling transition path time and rate measurements in reactions with large entropic barriers

    Makarov, Dmitrii E.


    Recent experiments and simulation studies showed that protein/DNA folding barriers inferred from folding rates or from potentials of mean force are often much higher than the barriers estimated from the distributions of transition path times. Here a toy model is used to explain a possible origin of this effect: It is shown that when the transition in question involves an entropic barrier, the one-dimensional Langevin model commonly used to interpret experimental data, while adequately predicting the transition rate, fails to describe the properties of the subset of the trajectories that form the transition path ensemble; the latter may still be describable in terms of a one-dimensional model, but with a different potential, just as observed experimentally.

  16. Modeling Propagation of Gas Path Damage

    National Aeronautics and Space Administration — This paper describes how damage propagation can be tracked and modeled for a range of fault modes in some modules of commercial high bypass aircraft engines. To that...

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

    Vogt-Geisse, Stefan


    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

  18. Atomic-level insights in optimizing reaction paths for hydroformylation reaction over Rh/CoO single-atom catalyst.

    Wang, Liangbing; Zhang, Wenbo; Wang, Shenpeng; Gao, Zehua; Luo, Zhiheng; Wang, Xu; Zeng, Rui; Li, Aowen; Li, Hongliang; Wang, Menglin; Zheng, Xusheng; Zhu, Junfa; Zhang, Wenhua; Ma, Chao; Si, Rui; Zeng, Jie


    Rh-based heterogeneous catalysts generally have limited selectivity relative to their homogeneous counterparts in hydroformylation reactions despite of the convenience of catalyst separation in heterogeneous catalysis. Here, we develop CoO-supported Rh single-atom catalysts (Rh/CoO) with remarkable activity and selectivity towards propene hydroformylation. By increasing Rh mass loading, isolated Rh atoms switch to aggregated clusters of different atomicity. During the hydroformylation, Rh/CoO achieves the optimal selectivity of 94.4% for butyraldehyde and the highest turnover frequency number of 2,065 h(-1) among the obtained atomic-scale Rh-based catalysts. Mechanistic studies reveal that a structural reconstruction of Rh single atoms in Rh/CoO occurs during the catalytic process, facilitating the adsorption and activation of reactants. In kinetic view, linear products are determined as the dominating products by analysing reaction paths deriving from the two most stable co-adsorbed configurations. As a bridge of homogeneous and heterogeneous catalysis, single-atom catalysts can be potentially applied in other industrial reactions.

  19. Atomic-level insights in optimizing reaction paths for hydroformylation reaction over Rh/CoO single-atom catalyst

    Wang, Liangbing; Zhang, Wenbo; Wang, Shenpeng; Gao, Zehua; Luo, Zhiheng; Wang, Xu; Zeng, Rui; Li, Aowen; Li, Hongliang; Wang, Menglin; Zheng, Xusheng; Zhu, Junfa; Zhang, Wenhua; Ma, Chao; Si, Rui; Zeng, Jie


    Rh-based heterogeneous catalysts generally have limited selectivity relative to their homogeneous counterparts in hydroformylation reactions despite of the convenience of catalyst separation in heterogeneous catalysis. Here, we develop CoO-supported Rh single-atom catalysts (Rh/CoO) with remarkable activity and selectivity towards propene hydroformylation. By increasing Rh mass loading, isolated Rh atoms switch to aggregated clusters of different atomicity. During the hydroformylation, Rh/CoO achieves the optimal selectivity of 94.4% for butyraldehyde and the highest turnover frequency number of 2,065 h-1 among the obtained atomic-scale Rh-based catalysts. Mechanistic studies reveal that a structural reconstruction of Rh single atoms in Rh/CoO occurs during the catalytic process, facilitating the adsorption and activation of reactants. In kinetic view, linear products are determined as the dominating products by analysing reaction paths deriving from the two most stable co-adsorbed configurations. As a bridge of homogeneous and heterogeneous catalysis, single-atom catalysts can be potentially applied in other industrial reactions.

  20. Optimal control of a Cope rearrangement by coupling the reaction path to a dissipative bath or a second active mode

    Chenel, A. [Laboratoire de Chimie Physique, UMR 8000 and CNRS, Université Paris-Sud, F-91405 Orsay (France); Meier, C. [Laboratoire Collisions, Agrégats, Réactivité, UMR 5589, IRSAMC, Université Paul Sabatier, F-31062 Toulouse (France); Dive, G. [Centre d’Ingéniérie des Protéines, Université de Liège, Sart Tilman, B6, B-4000 Liège (Belgium); Desouter-Lecomte, M. [Laboratoire de Chimie Physique, UMR 8000 and CNRS, Université Paris-Sud, F-91405 Orsay (France); Département de Chimie, Université de Liège, Bât B6c, Sart Tilman, B4000 Liège (Belgium)


    We compare the strategy found by the optimal control theory in a complex molecular system according to the active subspace coupled to the field. The model is the isomerization during a Cope rearrangement of Thiele’s ester that is the most stable dimer obtained by the dimerization of methyl-cyclopentadienenylcarboxylate. The crudest partitioning consists in retaining in the active space only the reaction coordinate, coupled to a dissipative bath of harmonic oscillators which are not coupled to the field. The control then fights against dissipation by accelerating the passage across the transition region which is very wide and flat in a Cope reaction. This mechanism has been observed in our previous simulations [Chenel et al., J. Phys. Chem. A 116, 11273 (2012)]. We compare here, the response of the control field when the reaction path is coupled to a second active mode. Constraints on the integrated intensity and on the maximum amplitude of the fields are imposed limiting the control landscape. Then, optimum field from one-dimensional simulation cannot provide a very high yield. Better guess fields based on the two-dimensional model allow the control to exploit different mechanisms providing a high control yield. By coupling the reaction surface to a bath, we confirm the link between the robustness of the field against dissipation and the time spent in the delocalized states above the transition barrier.

  1. Reaction path and crystallograpy of cobalt silicide formation on silicon(001) by reaction deposition epitaxy

    Lim, Chong Wee

    CaF2-structure CoSi2 layers were formed on Si(001) by reactive deposition epitaxy (RDE) and compared with CoSi2 layers obtained by conventional solid phase growth (SPG). In the case of RDE, CoSi 2 formation occurred during Co deposition at elevated temperature while for SPG, Co was deposited at 25°C and silicidation took place during subsequent annealing. My results demonstrate that RDE CoSi2 layers are epitaxial with a cube-on-cube relationship, 001CoSi2 ‖001Si and 100CoSi2 ‖100 Si . In contrast, SPG films are polycrystalline with a mixed 111/002/022/112 orientation. I attribute the striking difference to rapid Co diffusion during RDE for which the high Co/Si reactivity gives rise to a flux-limited reaction resulting in the direct formation of the disilicide phase. Initial formation of CoSi2(001) follows the Volmer-Weber mode with two families of island shapes: inverse pyramids and platelets. The rectangular-based pyramidal islands extend along orthogonal directions, bounded by four {111} CoSi2/Si interfaces, and grow with a cube-on-cube orientation with respect to Si(001). Platelet-shaped islands are bounded across their long directions by {111} twin planes and their narrow directions by 511CoSi2 ‖111Si interfaces. The top and bottom surfaces are {22¯1}, with 22¯1 CoSi2‖001 Si , and {1¯1¯1}, with 1¯1¯ 1CoSi2‖ 11¯1Si , respectively. The early stages of film growth (tCo ≤ 13 A) are dominated by the twinned platelets due to a combination of higher nucleation rates and rapid elongation along preferred directions. However, at tCo ≥ 13 A, island coalescence becomes significant as orthogonal platelets intersect and block elongation along fast growth directions. Further island growth becomes dominated by the untwinned islands. I show that high-flux low-energy Ar+ ion irradiation during RDE growth dramatically increases the area fraction of untwinned regions from 0.17 in films grown under standard magnetically balanced conditions in which the ratio

  2. Design Change Model for Effective Scheduling Change Propagation Paths

    Zhang, Hai-Zhu; Ding, Guo-Fu; Li, Rong; Qin, Sheng-Feng; Yan, Kai-Yin


    Changes in requirements may result in the increasing of product development project cost and lead time, therefore, it is important to understand how requirement changes propagate in the design of complex product systems and be able to select best options to guide design. Currently, a most approach for design change is lack of take the multi-disciplinary coupling relationships and the number of parameters into account integrally. A new design change model is presented to systematically analyze and search change propagation paths. Firstly, a PDS-Behavior-Structure-based design change model is established to describe requirement changes causing the design change propagation in behavior and structure domains. Secondly, a multi-disciplinary oriented behavior matrix is utilized to support change propagation analysis of complex product systems, and the interaction relationships of the matrix elements are used to obtain an initial set of change paths. Finally, a rough set-based propagation space reducing tool is developed to assist in narrowing change propagation paths by computing the importance of the design change parameters. The proposed new design change model and its associated tools have been demonstrated by the scheduling change propagation paths of high speed train's bogie to show its feasibility and effectiveness. This model is not only supportive to response quickly to diversified market requirements, but also helpful to satisfy customer requirements and reduce product development lead time. The proposed new design change model can be applied in a wide range of engineering systems design with improved efficiency.

  3. Transition path sampling with quantum/classical mechanics for reaction rates.

    Gräter, Frauke; Li, Wenjin


    Predicting rates of biochemical reactions through molecular simulations poses a particular challenge for two reasons. First, the process involves bond formation and/or cleavage and thus requires a quantum mechanical (QM) treatment of the reaction center, which can be combined with a more efficient molecular mechanical (MM) description for the remainder of the system, resulting in a QM/MM approach. Second, reaction time scales are typically many orders of magnitude larger than the (sub-)nanosecond scale accessible by QM/MM simulations. Transition path sampling (TPS) allows to efficiently sample the space of dynamic trajectories from the reactant to the product state without an additional biasing potential. We outline here the application of TPS and QM/MM to calculate rates for biochemical reactions, by means of a simple toy system. In a step-by-step protocol, we specifically refer to our implementation within the MD suite Gromacs, which we have made available to the research community, and include practical advice on the choice of parameters.

  4. Investigation at the atomic level of homologous enzymes reveals distinct reaction paths

    Zoi, Ioanna; Schwartz, Steven D.


    Bacterial enzymes Escherichia coli and Vibrio cholerae 5' -Methylthioadenosine nucleosidases (MTANs) have different binding affinities for the same transition state analogue. This was surprising as these enzymes share 60% sequence identity, have almost identical active sites and act under the same mechanism. We performed Transition Path Sampling simulations of both enzymes to reveal the atomic details of the catalytic chemical step, to explain the inhibitor affinity differences. Unlike EcMTAN, VcMTAN has multiple distinct transition states, which is an indication that multiple sets of coordinated protein motions can reach a transition state. We also identified the important residues that participate in each enzyme's reaction coordinate and explained their contribution. Subtle dynamic differences manifest in difference of reaction coordinate and transition state structure and also suggest that MTANs differ from most ribosyl transferases. As experimental approaches report averages regarding reaction coordinate information, this study offers, previously unavailable, detailed knowledge to the explanation of bacterial MTANs catalytic mechanism, and could have a significant impact on pharmaceutical design. We acknowledge the support of the National Institutes of Health through Grant GM068036.

  5. Evaluating status change of soil potassium from path model.

    Wenming He

    Full Text Available The purpose of this study is to determine critical environmental parameters of soil K availability and to quantify those contributors by using a proposed path model. In this study, plot experiments were designed into different treatments, and soil samples were collected and further analyzed in laboratory to investigate soil properties influence on soil potassium forms (water soluble K, exchangeable K, non-exchangeable K. Furthermore, path analysis based on proposed path model was carried out to evaluate the relationship between potassium forms and soil properties. Research findings were achieved as followings. Firstly, key direct factors were soil S, ratio of sodium-potassium (Na/K, the chemical index of alteration (CIA, Soil Organic Matter in soil solution (SOM, Na and total nitrogen in soil solution (TN, and key indirect factors were Carbonate (CO3, Mg, pH, Na, S, and SOM. Secondly, path model can effectively determine direction and quantities of potassium status changes between Exchangeable potassium (eK, Non-exchangeable potassium (neK and water-soluble potassium (wsK under influences of specific environmental parameters. In reversible equilibrium state of [Formula: see text], K balance state was inclined to be moved into β and χ directions in treatments of potassium shortage. However in reversible equilibrium of [Formula: see text], K balance state was inclined to be moved into θ and λ directions in treatments of water shortage. Results showed that the proposed path model was able to quantitatively disclose moving direction of K status and quantify its equilibrium threshold. It provided a theoretical and practical basis for scientific and effective fertilization in agricultural plants growth.

  6. Neuromorphic model of magnocellular and parvocellular visual paths: spatial resolution

    Aguirre, Rolando C [Departamento de Luminotecnia, Luz y Vision, FACET, Universidad Nacional de Tucuman, Tucuman (Argentina); Felice, Carmelo J [Departamento de BioingenierIa, FACET, Universidad Nacional de Tucuman Argentina, Tucuman (Argentina); Colombo, Elisa M [Departamento de Luminotecnia, Luz y Vision, FACET, Universidad Nacional de Tucuman, Tucuman (Argentina)


    Physiological studies of the human retina show the existence of at least two visual information processing channels, the magnocellular and the parvocellular ones. Both have different spatial, temporal and chromatic features. This paper focuses on the different spatial resolution of these two channels. We propose a neuromorphic model, so that they match the retina's physiology. Considering the Deutsch and Deutsch model (1992), we propose two configurations (one for each visual channel) of the connection between the retina's different cell layers. The responses of the proposed model have similar behaviour to those of the visual cells: each channel has an optimum response corresponding to a given stimulus size which decreases for larger or smaller stimuli. This size is bigger for the magno path than for the parvo path and, in the end, both channels produce a magnifying of the borders of a stimulus.

  7. Catalytic mechanism of α-phosphate attack in dUTPase is revealed by X-ray crystallographic snapshots of distinct intermediates, 31P-NMR spectroscopy and reaction path modelling.

    Barabás, Orsolya; Németh, Veronika; Bodor, Andrea; Perczel, András; Rosta, Edina; Kele, Zoltán; Zagyva, Imre; Szabadka, Zoltán; Grolmusz, Vince I; Wilmanns, Matthias; Vértessy, Beáta G


    Enzymatic synthesis and hydrolysis of nucleoside phosphate compounds play a key role in various biological pathways, like signal transduction, DNA synthesis and metabolism. Although these processes have been studied extensively, numerous key issues regarding the chemical pathway and atomic movements remain open for many enzymatic reactions. Here, using the Mason-Pfizer monkey retrovirus dUTPase, we study the dUTPase-catalyzed hydrolysis of dUTP, an incorrect DNA building block, to elaborate the mechanistic details at high resolution. Combining mass spectrometry analysis of the dUTPase-catalyzed reaction carried out in and quantum mechanics/molecular mechanics (QM/MM) simulation, we show that the nucleophilic attack occurs at the α-phosphate site. Phosphorus-31 NMR spectroscopy ((31)P-NMR) analysis confirms the site of attack and shows the capability of dUTPase to cleave the dUTP analogue α,β-imido-dUTP, containing the imido linkage usually regarded to be non-hydrolyzable. We present numerous X-ray crystal structures of distinct dUTPase and nucleoside phosphate complexes, which report on the progress of the chemical reaction along the reaction coordinate. The presently used combination of diverse structural methods reveals details of the nucleophilic attack and identifies a novel enzyme-product complex structure.

  8. Path integral quantization of the relativistic Hopfield model

    Belgiorno, F; Piazza, F Dalla; Doronzo, M


    The path integral quantization method is applied to a relativistically covariant version of the Hopfield model, which represents a very interesting mesoscopic framework for the description of the interaction between quantum light and dielectric quantum matter, with particular reference to the context of analogue gravity. In order to take into account the constraints occurring in the model, we adopt the Faddeev-Jackiw approach to constrained quantization in the path integral formalism. In particular we demonstrate that the propagator obtained with the Faddeev-Jackiw approach is equivalent to the one which, in the framework of Dirac canonical quantization for constrained systems, can be directly computed as the vacuum expectation value of the time ordered product of the fields. Our analysis also provides an explicit example of quantization of the electromagnetic field in a covariant gauge and coupled with the polarization field, which is a novel contribution to the literature on the Faddeev-Jackiw procedure.

  9. Comparative Study of Path Loss Models in Different Environments

    Tilotma Yadav,


    Full Text Available By using propagation path models to estimate the received signal level as a function of distance, it becomes possible to predict the SNR for a mobile communication system. Both theoretical andmeasurement-based propagation models indicate that average received signal power decreases logarithmically with distance. For comparative analysis we use Okumura’s model, Hata model, COST231 Extension to Hata model,ECEC-33 model,SUI model along with the practical data. Most of these models are based on a systematic interpretation of theoretical data service area like urban(Built-up city or largetown crowded with large buildings, suburban (having some obstacles near the mobile radio car, but still not very congested and rural (No obstacles like tall trees or buildings like farm-land, rice field, open fields in INDIA at 900MHz & 1800MHz frequency .

  10. Modeling of tool path for the CNC sheet cutting machines

    Petunin, Aleksandr A.


    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.

  11. Density Functional Theory and MP2 Calculations of the Transition States and Reaction Paths on Coupling Reaction of Methane through Plasma

    YANG,En-Cui(杨恩翠); ZHAO,Xiao-Jun(赵小军); TIAN,Peng(田鹏); HAO,Jin-Ku(郝金库)


    The two possible reaction paths of producing ethane on coupling reaction of methane through plasma were theoretically investigated by B3LYP and MP2 methods with 6-311G* respectively and further compared with the previous results calculated from B3LYP/6-31G*.The new investigated results consistently confirmed the previous conclusion.And the influences of the calculation methods and basis sets on the calculated results were also discussed.

  12. Regularization Paths for Generalized Linear Models via Coordinate Descent

    Jerome Friedman


    Full Text Available We develop fast algorithms for estimation of generalized linear models with convex penalties. The models include linear regression, two-class logistic regression, and multi- nomial regression problems while the penalties include ℓ1 (the lasso, ℓ2 (ridge regression and mixtures of the two (the elastic net. The algorithms use cyclical coordinate descent, computed along a regularization path. The methods can handle large problems and can also deal efficiently with sparse features. In comparative timings we find that the new algorithms are considerably faster than competing methods.

  13. Nonstatistical dynamics on potentials exhibiting reaction path bifurcations and valley-ridge inflection points

    Collins, Peter; Ezra, Gregory S; Wiggins, Stephen


    We study reaction dynamics on a model potential energy surface exhibiting post-transition state bifurcation in the vicinity of a valley ridge inflection point. We compute fractional yields of products reached after the VRI region is traversed, both with and without dissipation. It is found that apparently minor variations in the potential lead to significant changes in the reaction dynamics. Moreover, when dissipative effects are incorporated, the product ratio depends in a complicated and highly non-monotonic fashion on the dissipation parameter. Dynamics in the vicinity of the VRI point itself play essentially no role in determining the product ratio, except in the highly dissipative regime.

  14. On Models of Nonlinear Evolution Paths in Adiabatic Quantum Algorithms

    SUN Jie; LU Song-Feng; Samuel L.Braunstein


    In this paper,we study two different nonlinear interpolating paths in adiabatic evolution algorithms for solving a particular class of quantum search problems where both the initial and final Hamiltonian are one-dimensional projector Hamiltonians on the corresponding ground state.If the overlap between the initial state and final state of the quantum system is not equal to zero,both of these models can provide a constant time speedup over the usual adiabatic algorithms by increasing some another corresponding "complexity".But when the initial state has a zero overlap with the solution state in the problem,the second model leads to an infinite time complexity of the algorithm for whatever interpolating functions being applied while the first one can still provide a constant running time.However,inspired by a related reference,a variant of the first model can be constructed which also fails for the problem when the overlap is exactly equal to zero if we want to make up the "intrinsic" fault of the second model — an increase in energy.Two concrete theorems are given to serve as explanations why neither of these two models can improve the usual adiabatic evolution algorithms for the phenomenon above.These just tell us what should be noted when using certain nonlinear evolution paths in adiabatic quantum algorithms for some special kind of problems.

  15. Conservation laws and path-independent integrals in mechanical-diffusion-electrochemical reaction coupling system

    Yu, Pengfei; Wang, Hailong; Chen, Jianyong; Shen, Shengping


    In this study, the conservation laws οf dissipative mechanical-diffusion-electrochemical reaction system are systematically obtained based on Noether's theorem. According to linear, irreversible thermodynamics, dissipative phenomena can be described by an irreversible force and an irreversible flow. Additionally, the Lagrange function, L and the generalized Hamilton least-action principle are proposed to be used to obtain the conservation integrals. A group of these integrals, including the J-, M-, and L-integrals, can be then obtained using the classical Noether approach for dissipative processes. The relation between the J-integral and the energy release rate is illustrated. The path-independence of the J-integral is then proven. The J-integral, derived based on Noether's theorem, is a line integral, contrary to the propositions of existing published works that describe it both as a line and an area integral. Herein, we prove that the outcomes are identical, and identify the physical meaning of the area integral, a concept that was not explained previously. To show that the J-integral can dominate the distribution of the corresponding field quantities, an example of a partial, stress-diffusion coupling process is disscussed.

  16. The solubility of (Ba,Sr)SO 4 precipitates: Thermodynamic equilibrium and reaction path analysis

    Felmy, Andrew R.; Rai, Dhanpat; Moore, Dean A.


    The solubility of (Ba,Sr)SO 4 precipitates, varying in SrSO 4 mole fraction from 0.05-0.90, was investigated at room temperature with an equilibration period extending to almost three years. The data show that on or before 315 days of equilibration the precipitates reach a reversible equilibrium with the aqueous solution. The reversibility of this equilibrium was verified both by the attainment of steady-state concentrations with time and by heating the samples to perturb the equilibrium and then observing the slow return to the initial equilibrium state. The dissolution of the (Ba,Sr)SO 4 precipitates does not, in general, follow limiting reaction paths as defined by the Lippmann solutus or stoichiometric dissolution curves. In addition, activity coefficient calculations for the BaSO 4 and SrSO 4 components of the solid phase, using either total bulk analysis or near-surface analysis of the component mole fractions, do not satisfy the Gibbs-Duhem equation, demonstrating that a single solid-solution phase does not control both the aqueous Ba and Sr concentrations. Instead, our long-term equilibration data can be explained by the unavoidable formation of small amounts of barite and substitution of Sr into a solid-solution phase with the BaSO 4 component of the solid-solution phase never reaching thermodynamic equilibrium with the aqueous phase.

  17. Progress in microscopic direct reaction modeling of nucleon induced reactions

    Dupuis, M.; Bauge, E.; Hilaire, S.; Lechaftois, F.; Peru, S.; Pillet, N.; Robin, C. [CEA, DAM, DIF, Arpajon (France)


    A microscopic nuclear reaction model is applied to neutron elastic and direct inelastic scatterings, and pre-equilibrium reaction. The JLM folding model is used with nuclear structure information calculated within the quasi-particle random phase approximation implemented with the Gogny D1S interaction. The folding model for direct inelastic scattering is extended to include rearrangement corrections stemming from both isoscalar and isovector density variations occurring during a transition. The quality of the predicted (n,n), (n,n{sup '}), (n,xn) and (n,n{sup '}γ) cross sections, as well as the generality of the present microscopic approach, shows that it is a powerful tool that can help improving nuclear reactions data quality. Short- and long-term perspectives are drawn to extend the present approach to more systems, to include missing reactions mechanisms, and to consistently treat both structure and reaction problems. (orig.)

  18. Modelling Chemical Reasoning to Predict Reactions

    Segler, Marwin H S


    The ability to reason beyond established knowledge allows Organic Chemists to solve synthetic problems and to invent novel transformations. Here, we propose a model which mimics chemical reasoning and formalises reaction prediction as finding missing links in a knowledge graph. We have constructed a knowledge graph containing 14.4 million molecules and 8.2 million binary reactions, which represents the bulk of all chemical reactions ever published in the scientific literature. Our model outperforms a rule-based expert system in the reaction prediction task for 180,000 randomly selected binary reactions. We show that our data-driven model generalises even beyond known reaction types, and is thus capable of effectively (re-) discovering novel transformations (even including transition-metal catalysed reactions). Our model enables computers to infer hypotheses about reactivity and reactions by only considering the intrinsic local structure of the graph, and because each single reaction prediction is typically ac...

  19. Constrained approximation of effective generators for multiscale stochastic reaction networks and application to conditioned path sampling

    Cotter, Simon L.


    Efficient analysis and simulation of multiscale stochastic systems of chemical kinetics is an ongoing area for research, and is the source of many theoretical and computational challenges. In this paper, we present a significant improvement to the constrained approach, which is a method for computing effective dynamics of slowly changing quantities in these systems, but which does not rely on the quasi-steady-state assumption (QSSA). The QSSA can cause errors in the estimation of effective dynamics for systems where the difference in timescales between the "fast" and "slow" variables is not so pronounced. This new application of the constrained approach allows us to compute the effective generator of the slow variables, without the need for expensive stochastic simulations. This is achieved by finding the null space of the generator of the constrained system. For complex systems where this is not possible, or where the constrained subsystem is itself multiscale, the constrained approach can then be applied iteratively. This results in breaking the problem down into finding the solutions to many small eigenvalue problems, which can be efficiently solved using standard methods. Since this methodology does not rely on the quasi steady-state assumption, the effective dynamics that are approximated are highly accurate, and in the case of systems with only monomolecular reactions, are exact. We will demonstrate this with some numerics, and also use the effective generators to sample paths of the slow variables which are conditioned on their endpoints, a task which would be computationally intractable for the generator of the full system.

  20. Randomized shortest-path problems: two related models.

    Saerens, Marco; Achbany, Youssef; Fouss, François; Yen, Luh


    This letter addresses the problem of designing the transition probabilities of a finite Markov chain (the policy) in order to minimize the expected cost for reaching a destination node from a source node while maintaining a fixed level of entropy spread throughout the network (the exploration). It is motivated by the following scenario. Suppose you have to route agents through a network in some optimal way, for instance, by minimizing the total travel cost-nothing particular up to now-you could use a standard shortest-path algorithm. Suppose, however, that you want to avoid pure deterministic routing policies in order, for instance, to allow some continual exploration of the network, avoid congestion, or avoid complete predictability of your routing strategy. In other words, you want to introduce some randomness or unpredictability in the routing policy (i.e., the routing policy is randomized). This problem, which will be called the randomized shortest-path problem (RSP), is investigated in this work. The global level of randomness of the routing policy is quantified by the expected Shannon entropy spread throughout the network and is provided a priori by the designer. Then, necessary conditions to compute the optimal randomized policy-minimizing the expected routing cost-are derived. Iterating these necessary conditions, reminiscent of Bellman's value iteration equations, allows computing an optimal policy, that is, a set of transition probabilities in each node. Interestingly and surprisingly enough, this first model, while formulated in a totally different framework, is equivalent to Akamatsu's model ( 1996 ), appearing in transportation science, for a special choice of the entropy constraint. We therefore revisit Akamatsu's model by recasting it into a sum-over-paths statistical physics formalism allowing easy derivation of all the quantities of interest in an elegant, unified way. For instance, it is shown that the unique optimal policy can be obtained by

  1. Path Partition in Directed Graph – Modeling and Optimization

    Issam Abdel Kader


    Full Text Available The concept of graph theory is therefore perfectly suitable to structure a problem in its initial analysis phases since a graph is the most general mathematical object. At the structural level, the nodes represent the objects, the variables… and the arc forms the binary relation of influence among them. Many real problems can be modeled as path partition in directed graph that played particular role in the operation of arranging a set of nodes especially in case of directed acyclic graph (DAG. We encounter such graph in schedule problems, the analysis of language structure, the probability theory, the game theory, compilers…. Moreover managerial problem can be modeled as acyclic graphs, also the potential problem has a suitable solution if and only if the graph is acyclic.

  2. Autonomous guided vehicles methods and models for optimal path planning

    Fazlollahtabar, Hamed


      This book provides readers with extensive information on path planning optimization for both single and multiple Autonomous Guided Vehicles (AGVs), and discusses practical issues involved in advanced industrial applications of AGVs. After discussing previously published research in the field and highlighting the current gaps, it introduces new models developed by the authors with the goal of reducing costs and increasing productivity and effectiveness in the manufacturing industry. The new models address the increasing complexity of manufacturing networks, due for example to the adoption of flexible manufacturing systems that involve automated material handling systems, robots, numerically controlled machine tools, and automated inspection stations, while also considering the uncertainty and stochastic nature of automated equipment such as AGVs. The book discusses and provides solutions to important issues concerning the use of AGVs in the manufacturing industry, including material flow optimization with A...

  3. Using a reflection model for modeling the dynamic feedback path of digital hearing aids

    Ma, Guilin; Gran, Fredrik; Jacobsen, Finn;


    Feedback whistling is one of the severe problems with hearing aids, especially in dynamic situations when the users hug, pick up a telephone, etc. This paper investigates the properties of the dynamic feedback paths of digital hearing aids and proposes a model based on a reflection assumption...... gain. The method is also extended to dual-microphone hearing aids to assess the possibility of relating the two dynamic feedback paths through the reflection model. However, it is found that in a complicated acoustic environment, the relation between the two feedback paths can be very intricate...

  4. A Commentary on the Relationship between Model Fit and Saturated Path Models in Structural Equation Modeling Applications

    Raykov, Tenko; Lee, Chun-Lung; Marcoulides, George A.; Chang, Chi


    The relationship between saturated path-analysis models and their fit to data is revisited. It is demonstrated that a saturated model need not fit perfectly or even well a given data set when fit to the raw data is examined, a criterion currently frequently overlooked by researchers utilizing path analysis modeling techniques. The potential of…

  5. Formulation of a Network and the Study of Reaction Paths for the Sustainable Reduction of CO2 Emissions

    Frauzem, Rebecca; Kongpanna, Pichayapan; Roh, Kosan

    carbonate (DMC) [2]. In this work, through a computer-aided framework for process network synthesis-design, a network of conversion processes that all use emitted CO2 is investigated. CO2 is emitted into the environment from various sources: power generation, industrial processes, transportation...... and commercial processes. Within these there are high-purity emissions and low-purity emissions. Rather than sending these to the atmosphere, it is possible to collect them and use them for other purposes. Targeting some of the largest contributors: power generation, manufacturing, chemical industry...... through the reactions. Studies and detailed simulations have been performed on CO2 conversion to methanol, synthesis gas processes, dimethyl carbonate production, and other processes. The detailed simulations are performed on the paths that are selected based on basic calculations on each path. Then...

  6. Stationary Conditions of the Electron Density Along the Reaction Path: Connection with Conceptual DFT and Information Theory.

    Gonzalez, Carlos A; Squitieri, Emilio; Franco, Hector J; Rincon, Luis C


    The Kohn-Sham density functional theory (DFT) formalism has been used to investigate the influence of the stationary behavior of the electron density (ρ(r⃗;s)) along a minimum energy path on the corresponding stationary conditions observed in the total potential energy of the reactive system, information theory measures (Shannon information entropy and Onicescu information energy), and chemical reactivity indexes (the chemical hardness). The theoretical treatment presented in this work, combined with DFT calculations on 3 different test reactions: Ḣ' + H2, Ḣ' + CH4 and H(-) + CH4, suggest that for any reactive system, properties that can be cast as a functional of the electron density, must exhibit stationary points along the IRC path modulated by the corresponding stationary behavior of the electron density.

  7. Modelling Chemical Reasoning to Predict Reactions

    Segler, Marwin H. S.; Waller, Mark P.


    The ability to reason beyond established knowledge allows Organic Chemists to solve synthetic problems and to invent novel transformations. Here, we propose a model which mimics chemical reasoning and formalises reaction prediction as finding missing links in a knowledge graph. We have constructed a knowledge graph containing 14.4 million molecules and 8.2 million binary reactions, which represents the bulk of all chemical reactions ever published in the scientific literature. Our model outpe...

  8. Model Checking Real Time Java Using Java PathFinder

    Lindstrom, Gary; Mehlitz, Peter C.; Visser, Willem


    The Real Time Specification for Java (RTSJ) is an augmentation of Java for real time applications of various degrees of hardness. The central features of RTSJ are real time threads; user defined schedulers; asynchronous events, handlers, and control transfers; a priority inheritance based default scheduler; non-heap memory areas such as immortal and scoped, and non-heap real time threads whose execution is not impeded by garbage collection. The Robust Software Systems group at NASA Ames Research Center has JAVA PATHFINDER (JPF) under development, a Java model checker. JPF at its core is a state exploring JVM which can examine alternative paths in a Java program (e.g., via backtracking) by trying all nondeterministic choices, including thread scheduling order. This paper describes our implementation of an RTSJ profile (subset) in JPF, including requirements, design decisions, and current implementation status. Two examples are analyzed: jobs on a multiprogramming operating system, and a complex resource contention example involving autonomous vehicles crossing an intersection. The utility of JPF in finding logic and timing errors is illustrated, and the remaining challenges in supporting all of RTSJ are assessed.

  9. Connectionist and diffusion models of reaction time.

    Ratcliff, R; Van Zandt, T; McKoon, G


    Two connectionist frameworks, GRAIN (J. L. McClelland, 1993) and brain-state-in-a-box (J. A. Anderson, 1991), and R. Ratcliff's (1978) diffusion model were evaluated using data from a signal detection task. Dependent variables included response probabilities, reaction times for correct and error responses, and shapes of reaction-time distributions. The diffusion model accounted for all aspects of the data, including error reaction times that had previously been a problem for all response-time models. The connectionist models accounted for many aspects of the data adequately, but each failed to a greater or lesser degree in important ways except for one model that was similar to the diffusion model. The findings advance the development of the diffusion model and show that the long tradition of reaction-time research and theory is a fertile domain for development and testing of connectionist assumptions about how decisions are generated over time.

  10. Chemical-reaction model for Mexican wave

    Nagatani, Takashi


    We present a chemical-reaction model to describe the Mexican wave ( La Ola) in football stadia. The spectator's action is described in terms of chemical reactions. The model is governed by three reaction rates k 1, k 2, and k3. We study the nonlinear waves on one- and two-dimensional lattices. The Mexican wave is formulated as a clockwise forwardly propagating wave. Waves are growing or disappear, depending on the values of reaction rates. In the specific case of k1= k2= k3=1, the nonlinear-wave equation produces a propagating pulse like soliton.

  11. Secondary Path Modeling Method for Active Noise Control of Power Transformer

    Zhao, Tong; Liang, Jiabi; Liang, Yuanbin; Wang, Lixin; Pei, Xiugao; Li, Peng

    The accuracy of the secondary path modeling is critical to the stability of active noise control system. On condition of knowing the input and output of the secondary path, system identification theory can be used to identify the path. Based on the experiment data, correlation analysis is adopted to eliminate the random noise and nonlinear harmonic in the output data in order to obtain the accurate frequency characteristic of the secondary path. After that, Levy's Method is applied to identify the transfer function of the path. Computer simulation results are given respectively, both showing the proposed off-line modeling method is feasible and applicable. At last, Levy's Method is used to attain an accurate secondary path model in the active control of transformer noise experiment and achieves to make the noise sound level decrease about 10dB.

  12. Monte Carlo path sampling approach to modeling aeolian sediment transport

    Hardin, E. J.; Mitasova, H.; Mitas, L.


    Coastal communities and vital infrastructure are subject to coastal hazards including storm surge and hurricanes. Coastal dunes offer protection by acting as natural barriers from waves and storm surge. During storms, these landforms and their protective function can erode; however, they can also erode even in the absence of storms due to daily wind and waves. Costly and often controversial beach nourishment and coastal construction projects are common erosion mitigation practices. With a more complete understanding of coastal morphology, the efficacy and consequences of anthropogenic activities could be better predicted. Currently, the research on coastal landscape evolution is focused on waves and storm surge, while only limited effort is devoted to understanding aeolian forces. Aeolian transport occurs when the wind supplies a shear stress that exceeds a critical value, consequently ejecting sand grains into the air. If the grains are too heavy to be suspended, they fall back to the grain bed where the collision ejects more grains. This is called saltation and is the salient process by which sand mass is transported. The shear stress required to dislodge grains is related to turbulent air speed. Subsequently, as sand mass is injected into the air, the wind loses speed along with its ability to eject more grains. In this way, the flux of saltating grains is itself influenced by the flux of saltating grains and aeolian transport becomes nonlinear. Aeolian sediment transport is difficult to study experimentally for reasons arising from the orders of magnitude difference between grain size and dune size. It is difficult to study theoretically because aeolian transport is highly nonlinear especially over complex landscapes. Current computational approaches have limitations as well; single grain models are mathematically simple but are computationally intractable even with modern computing power whereas cellular automota-based approaches are computationally efficient

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

    Badin, E. J.; Calvin, M.


    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.

  14. Theoretical characterization of the minimum energy path for the reaction H + O2 to HO2(asterisk) to HO + O

    Walch, Stephen P.; Rohlfing, Celeste Mcmichael; Melius, Carl F.; Bauschlicher, Charles W., Jr.


    The potential energy surface for the H + O2 to HO2(asterisk) to HO + O reaction has been investigated in the region of the minimum energy path using CASSCF/contracted CI (CCI) calculations with a large basis set. The results show no barrier for the addition of an H atom to O2, in agreement with previous studies. A crossing between the surface for electrostatic (OH dipole-O quadrupole) interaction and that for the formation of an O-O chemical bond, at r(infinity) of about 5.5 a(0), results in a small (about 0.5 kcal/mol) barrier.

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

    Badin, Elmer J.; Calvin, Melvin


    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.

  16. Causal Modeling--Path Analysis a New Trend in Research in Applied Linguistics

    Rastegar, Mina


    This article aims at discussing a new statistical trend in research in applied linguistics. This rather new statistical procedure is causal modeling--path analysis. The article demonstrates that causal modeling--path analysis is the best statistical option to use when the effects of a multitude of L2 learners' variables on language achievement are…

  17. Kinetics of Model Reactions for Interfacial Polymerization

    Henry Hall


    Full Text Available To model the rates of interfacial polycondensations, the rates of reaction of benzoyl chloride and methyl chloroformate with various aliphatic monoamines in acetonitrile were determined at 25 °C. Buffering with picric acid slowed these extremely fast reactions so the rate constants could be determined from the rate of disappearance of picrate ion. The rates of the amine reactions correlated linearly with their Swain-Scott nucleophilicities.

  18. KEGG-PATH: Kyoto encyclopedia of genes and genomes-based pathway analysis using a path analysis model.

    Du, Junli; Yuan, Zhifa; Ma, Ziwei; Song, Jiuzhou; Xie, Xiaoli; Chen, Yulin


    The dynamic impact approach (DIA) represents an alternative to overrepresentation analysis (ORA) for functional analysis of time-course experiments or those involving multiple treatments. The DIA can be used to estimate the biological impact of the differentially expressed genes (DEGs) associated with particular biological functions, for example, as represented by the Kyoto encyclopedia of genes and genomes (KEGG) annotations. However, the DIA does not take into account the correlated dependence structure of the KEGG pathway hierarchy. We have developed herein a path analysis model (KEGG-PATH) to subdivide the total effect of each KEGG pathway into the direct effect and indirect effect by taking into account not only each KEGG pathway itself, but also the correlation with its related pathways. In addition, this work also attempts to preliminarily estimate the impact direction of each KEGG pathway by a gradient analysis method from principal component analysis (PCA). As a result, the advantage of the KEGG-PATH model is demonstrated through the functional analysis of the bovine mammary transcriptome during lactation.

  19. The effect of PLS regression in PLS path model estimation when multicollinearity is present

    Nielsen, Rikke; Kristensen, Kai; Eskildsen, Jacob

    PLS path modelling has previously been found to be robust to multicollinearity both between latent variables and between manifest variables of a common latent variable (see e.g. Cassel et al. (1999), Kristensen, Eskildsen (2005), Westlund et al. (2008)). However, most of the studies investigate...... models with relatively few variables and very simple dependence structures compared to the models that are often estimated in practical settings. A recent study by Nielsen et al. (2009) found that when model structure is more complex, PLS path modelling is not as robust to multicollinearity between...... latent variables as previously assumed. A difference in the standard error of path coefficients of as much as 83% was found between moderate and severe levels of multicollinearity. Large differences were found not only for large path coefficients, but also for small path coefficients and in some cases...

  20. Atomic-scale study of transformation paths in unmixing and ordering reactions

    Blavette, D.; Pareige-Schmuck, C.; Danoix, F. [CNRS, Mont Saint Aignan (France). Fac. des Sci. de Rouen; Stiller, K.


    The tomographic atom-probe (TAP) is a new high resolution nanoanalytical microscope, which provides three-dimensional maps of chemical heterogeneities in a metallic material on a near-atomic scale. Application of the TAP to unmixing and ordering in metallic alloys is discussed and illustrated through various examples (spinodal decomposition in FeCr ferritic phases, nucleation and growth of LI{sub 2} ordered precipitates in nickel based alloys, precipitation in maraging steels). The role of the TAP in the investigation of transformation paths in these systems is discussed. (orig.). 17 refs.

  1. A Full Disturbance Model for Reaction Wheels

    Le, M.P.; Ellenbroek, Marcellinus Hermannus Maria; Seiler, R; van Put, P.; Cottaar, E.J.E.


    Reaction wheels are rotating devices used for the attitude control of spacecraft. However, reaction wheels also generate undesired disturbances in the form of vibrations, which may have an adverse effect on the pointing accuracy and stability of spacecraft (optical) payloads. A disturbance model for

  2. Modeling of turbulent chemical reaction

    Chen, J.-Y.


    Viewgraphs are presented on modeling turbulent reacting flows, regimes of turbulent combustion, regimes of premixed and regimes of non-premixed turbulent combustion, chemical closure models, flamelet model, conditional moment closure (CMC), NO(x) emissions from turbulent H2 jet flames, probability density function (PDF), departures from chemical equilibrium, mixing models for PDF methods, comparison of predicted and measured H2O mass fractions in turbulent nonpremixed jet flames, experimental evidence of preferential diffusion in turbulent jet flames, and computation of turbulent reacting flows.

  3. Coherent-state path integral versus coarse-grained effective stochastic equation of motion: From reaction diffusion to stochastic sandpiles.

    Wiese, Kay Jörg


    We derive and study two different formalisms used for nonequilibrium processes: the coherent-state path integral, and an effective, coarse-grained stochastic equation of motion. We first study the coherent-state path integral and the corresponding field theory, using the annihilation process A+A→A as an example. The field theory contains counterintuitive quartic vertices. We show how they can be interpreted in terms of a first-passage problem. Reformulating the coherent-state path integral as a stochastic equation of motion, the noise generically becomes imaginary. This renders it not only difficult to interpret, but leads to convergence problems at finite times. We then show how alternatively an effective coarse-grained stochastic equation of motion with real noise can be constructed. The procedure is similar in spirit to the derivation of the mean-field approximation for the Ising model, and the ensuing construction of its effective field theory. We finally apply our findings to stochastic Manna sandpiles. We show that the coherent-state path integral is inappropriate, or at least inconvenient. As an alternative, we derive and solve its mean-field approximation, which we then use to construct a coarse-grained stochastic equation of motion with real noise.

  4. Numerical Method for Modeling the Constitutive Relationship of Sand under Different Stress Paths

    Ren Qingyang; Wang Jingtao


    A numerical method was used in order to establish the constitutive relationship of sands under different stress paths. Firstly, based on the numerical method modeling the constitutive law of sands, the elastoplastic constitutive relationship of sand was established for three paths: the constant proportion of principle stress path, the conventional triaxial compression (CTC) path, and the p=constant (TC) path. The yield lines of plastic volumetric strain and plastic generalized shear strain were given. Through visualization, the three dimensional surface of the stress-strain relationship in the whole stress field (p, q) obtained under the three paths was plotted. Also, by comparing the stress-strain surfaces and yield locus of the three stress paths, the differences were found to be obvious, which demonstrates that the influence of the stress paths on constitutive law was not neglected. The numerical modeling method overcame the difficulty of finding an analytical expression for plastic potential. The results simulated the experimental data with an accuracy of 90 % on average, so the constitutive model established in this paper provides an effective constitutive equation for this kind of engineering, reflecting the effect of practical stress paths that occur in sands.

  5. Social Cognitive Model of College Satisfaction: A Test of Measurement and Path Models

    Feldt, Ronald C.


    The study examined a model that integrates social-cognitive and trait-personality constructs to examine two domains of college satisfaction. Direct and indirect effects were observed for conscientiousness, perception of institutional resources, self-efficacy, and goal progress. Paths differed for personal and institutional satisfaction. Most…

  6. Latent variable models an introduction to factor, path, and structural equation analysis

    Loehlin, John C


    This fourth edition introduces multiple-latent variable models by utilizing path diagrams to explain the underlying relationships in the models. The book is intended for advanced students and researchers in the areas of social, educational, clinical, ind

  7. Cartographic modeling of snow avalanche path location within Glacier National Park, Montana

    Walsh, Stephen J.; Brown, Daniel G.; Bian, Ling; Butler, David R.


    Geographic information system (GIS) techniques were applied to the study of snow-avalanche path location within Glacier National Park, Montana. Aerial photointerpretation and field surveys confirmed the location of 121 avalanche paths within the selected study area. Spatial and nonspatial information on each path were integrated using the ARC/INFO GIS. Lithologic, structural, hydrographic, topographic, and land-cover impacts on path location were analyzed. All path frequencies within variable classes were normalized by the area of class occurrence relative to the total area of the study area and were added to the morphometric information contained within INFO tables. The normalized values for each GIS coverage were used to cartographically model, by means of composite factor weightings, avalanche path locations.

  8. Cartographic modeling of snow avalanche path location within Glacier National Park, Montana

    Walsh, Stephen J.; Brown, Daniel G.; Bian, Ling; Butler, David R.


    Geographic information system (GIS) techniques were applied to the study of snow-avalanche path location within Glacier National Park, Montana. Aerial photointerpretation and field surveys confirmed the location of 121 avalanche paths within the selected study area. Spatial and nonspatial information on each path were integrated using the ARC/INFO GIS. Lithologic, structural, hydrographic, topographic, and land-cover impacts on path location were analyzed. All path frequencies within variable classes were normalized by the area of class occurrence relative to the total area of the study area and were added to the morphometric information contained within INFO tables. The normalized values for each GIS coverage were used to cartographically model, by means of composite factor weightings, avalanche path locations.

  9. Polarity controlled reaction path and kinetics of thermal cis-to-trans isomerization of 4-aminoazobenzene.

    Joshi, Neeraj Kumar; Fuyuki, Masanori; Wada, Akihide


    Spectral and kinetic behavior of thermal cis-to-trans isomerization of 4-aminoazobenzene (AAB) is examined in various solvents of different polarities. In contrast to azobenzene (AB), it is found the rate of thermal isomerization of AAB is highly dependent on solvent polarity. Accelerated rates are observed in polar solvents as compared to nonpolar solvents. Moreover, a decrease in the barrier height with an increase in medium polarity is observed. Our observations suggest that inversion is the preferred pathway in cis-to-trans thermal isomerization in a nonpolar medium; however, in a polar medium, the isomerization path deviates from the inversion route and rotational behavior is incorporated. Differences in the kinetics and in mechanisms of isomerization in different media are rationalized in terms of modulation in barrier height by polarity of the medium and solute-solvent interaction. It is found that kinetics as well as the mechanism of thermal isomerization in AAB is controlled by the polarity of the medium.

  10. Tunable n-path notch filters for blocker suppression: modeling and verification

    Ghaffari, A.; Klumperink, Eric A.M.; Nauta, Bram


    N-path switched-RC circuits can realize filters with very high linearity and compression point while they are tunable by a clock frequency. In this paper, both differential and single-ended N-path notch filters are modeled and analyzed. Closed-form equations provide design equations for the main

  11. Mendelian Randomization versus Path Models: Making Causal Inferences in Genetic Epidemiology.

    Ziegler, Andreas; Mwambi, Henry; König, Inke R


    The term Mendelian randomization is popular in the current literature. The first aim of this work is to describe the idea of Mendelian randomization studies and the assumptions required for drawing valid conclusions. The second aim is to contrast Mendelian randomization and path modeling when different 'omics' levels are considered jointly. We define Mendelian randomization as introduced by Katan in 1986, and review its crucial assumptions. We introduce path models as the relevant additional component to the current use of Mendelian randomization studies in 'omics'. Real data examples for the association between lipid levels and coronary artery disease illustrate the use of path models. Numerous assumptions underlie Mendelian randomization, and they are difficult to be fulfilled in applications. Path models are suitable for investigating causality, and they should not be mixed up with the term Mendelian randomization. In many applications, path modeling would be the appropriate analysis in addition to a simple Mendelian randomization analysis. Mendelian randomization and path models use different concepts for causal inference. Path modeling but not simple Mendelian randomization analysis is well suited to study causality with different levels of 'omics' data. 2015 S. Karger AG, Basel.

  12. Reaction Mechanism for Direct Proton Transfer from Carbonic Acid to a Strong Base in Aqueous Solution II: Solvent Coordinate-Dependent Reaction Path.

    Daschakraborty, Snehasis; Kiefer, Philip M; Miller, Yifat; Motro, Yair; Pines, Dina; Pines, Ehud; Hynes, James T


    The protonation of methylamine base CH3NH2 by carbonic acid H2CO3 within a hydrogen (H)-bonded complex in aqueous solution was studied via Car-Parrinello dynamics in the preceding paper (Daschakraborty, S.; Kiefer, P. M.; Miller, Y.; Motro, Y.; Pines, D.; Pines, E.; Hynes, J. T. J. Phys. Chem. B 2016, DOI: 10.1021/acs.jpcb.5b12742). Here some important further details of the reaction path are presented, with specific emphasis on the water solvent's role. The overall reaction is barrierless and very rapid, on an ∼100 fs time scale, with the proton transfer (PT) event itself being very sudden (water solvent changes little until the actual PT occurrence; this results from the very strong driving force for the reaction, as indicated by the very favorable acid-protonated base ΔpKa difference. Further solvent rearrangement follows immediately the sudden PT's production of an incipient contact ion pair, stabilizing it by establishment of equilibrium solvation. The solvent water's short time scale ∼120 fs response to the incipient ion pair formation is primarily associated with librational modes and H-bond compression of water molecules around the carboxylate anion and the protonated base. This is consistent with this stabilization involving significant increase in H-bonding of hydration shell waters to the negatively charged carboxylate group oxygens' (especially the former H2CO3 donor oxygen) and the nitrogen of the positively charged protonated base's NH3(+).

  13. Location-based Mobile Relay Selection and Impact of Inaccurate Path Loss Model Parameters

    Nielsen, Jimmy Jessen; Madsen, Tatiana Kozlova; Schwefel, Hans-Peter


    In this paper we propose a relay selection scheme which uses collected location information together with a path loss model for relay selection, and analyze the performance impact of mobility and different error causes on this scheme. Performance is evaluated in terms of bit error rate...... in these situations. As the location-based scheme relies on a path loss model to estimate link qualities and select relays, the sensitivity with respect to inaccurate estimates of the unknown path loss model parameters is investigated. The parameter ranges that result in useful performance were found...

  14. Reaction phases and diffusion paths in SiC/metal systems

    Naka, M.; Fukai, T. [Osaka Univ., Osaka (Japan); Schuster, J.C. [Vienna Univ., Vienna (Austria)


    The interface structures between SiC and metal are reviewed at SiC/metal systems. Metal groups are divided to carbide forming metals and non-carbide forming metals. Carbide forming metals form metal carbide granular or zone at metal side, and metal silicide zone at SiC side. The further diffusion of Si and C from SiC causes the formation of T ternary phase depending metal. Non-carbide forming metals form silicide zone containing graphite or the layered structure of metal silicide and metal silicide containing graphite. The diffusion path between SiC and metal are formed along tie-lines connecting SiC and metal on the corresponding ternary Si-C-M system. The reactivity of metals is dominated by the forming ability of carbide or silicide. Te reactivity tendency of elements are discussed on the periodical table of elements, and Ti among elements shows the highest reactivity among carbide forming metals. For non-carbide forming metals the reactivity sequence of metals is Fe>Ni>Co. (orig.)

  15. Path Tracking Control of Automatic Parking Cloud Model considering the Influence of Time Delay

    Yiding Hua


    Full Text Available This paper establishes the kinematic model of the automatic parking system and analyzes the kinematic constraints of the vehicle. Furthermore, it solves the problem where the traditional automatic parking system model fails to take into account the time delay. Firstly, based on simulating calculation, the influence of time delay on the dynamic trajectory of a vehicle in the automatic parking system is analyzed under the transverse distance Dlateral between different target spaces. Secondly, on the basis of cloud model, this paper utilizes the tracking control of an intelligent path closer to human intelligent behavior to further study the Cloud Generator-based parking path tracking control method and construct a vehicle path tracking control model. Moreover, tracking and steering control effects of the model are verified through simulation analysis. Finally, the effectiveness and timeliness of automatic parking controller in the aspect of path tracking are tested through a real vehicle experiment.

  16. A Reaction-Based River/Stream Water Quality Model: Reaction Network Decomposition and Model Application


    This paper describes details of an automatic matrix decomposition approach for a reaction-based stream water quality model. The method yields a set of equilibrium equations, a set of kinetic-variable transport equations involving kinetic reactions only, and a set of component transport equations involving no reactions. Partial decomposition of the system of water quality constituent transport equations is performed via Gauss-Jordan column reduction of the reaction network by pivoting on equil...

  17. Free-path distribution and Knudsen-layer modeling for gaseous flows in the transition regime

    To, Quy Dong; Léonard, Céline; Lauriat, Guy


    In this paper, we use molecular dynamics (MD) simulations to study the mean free path distribution of nonequilibrium gases in micronanochannel and to model the Knudsen (Kn) layer effect. It is found that the mean free path is significantly reduced near the wall and rather insensitive to flow types (Poiseuille or Couette). The Cercignani relation between the mean free path and the viscosity is adopted to capture the velocity behavior of the special zone in the framework of the extended Navier-Stokes (NS) equations. MD simulations of flows are carried out at different Kn numbers. Results are then compared with the theoretical model.

  18. Path Dependence of the Quark Nonlocal Condensate within the Instanton Model

    Trevisan, L A; Tomio, Lauro; Tomio, Lauro


    Within the instanton liquid model, we study the dependence of the gauge invariant two--point quark correlator on the path used to perform the color parallel transport between two points in the Euclidean space.

  19. Strain-Path Modeling for Geo-Materials.


    feasible to obtain by measurement the stress-strain curves needed for reliable prediction of se smic sources. A subset of the same curves also prevails on a...explosive events is eviden - tly open to criticism, and some of that appears below. However, the aim of this paper is not to carp, but to map a more...curves needed for accurate prediction of motion at a given site are obtained by measuring stress along the kinds of strain paths already known to

  20. Curing Reaction Model of Epoxy Asphalt Binder

    QIAN Zhendong; CHEN Leilei; WANG Yaqi; SHEN Jialin


    In order to understand the strength developing law of the epoxy asphalt mixture,a curing reaction model of the epoxy asphalt binder was proposed based upon the thermokinetic analysis.Given some assumptions,the model was developed by applying the Kissinger law as well as Arrhenius equation,and the differential scanning calorimetry was performed for estimating the model parameters.To monitor the strength development of the epoxy asphalt mixture,a strength test program was employed and then results were compared to those produced from the proposed model.The comparative evaluation shows that a good consistency exists between the outputs from test program and the proposed model,indicating that the proposed model can be used effectively for simulating the curing reaction process for the epoxy asphalt binder and predicting the strength development for the epoxy asphalt mixture.

  1. Nonlinear control of the Salnikov model reaction

    Recke, Bodil; Jørgensen, Sten Bay


    This paper explores different nonlinear control schemes, applied to a simple model reaction. The model is the Salnikov model, consisting of two ordinary differential equations. The control strategies investigated are I/O-linearisation, Exact linearisation, exact linearisation combined with LQR...... and Control Lyapunov Functions (CLF's). The results show that based on the lowest possible cost function and shortest settling time, the exact linearisation performs marginally better than the other methods....

  2. A damage accumulation model for complex strain paths: Prediction of ductile failure in metals

    Lapovok, Rimma; Hodgson, D.


    The characterisation of strain path with respect to the directionality of defect formation is discussed. The criterion of non-monotonic strain path is used in the scalar and tensor models for damage accumulation and recovery. Comparable analysis of models and their verification has been obtained by simulation of crack initiation in a two-stage metal forming operation consisting of wire drawing followed by constrained upsetting.

  3. An Overview of Path Analysis: Mediation Analysis Concept in Structural Equation Modeling

    Jenatabadi, Hashem Salarzadeh


    This paper provides a tutorial discussion on path analysis structure with concept of structural equation modelling (SEM). The paper delivers an introduction to path analysis technique and explain to how to deal with analyzing the data with this kind of statistical methodology especially with a mediator in the research model. The intended audience is statisticians, mathematicians, or methodologists who either know about SEM or simple basic statistics especially in regression and linear/nonline...

  4. Dynamical Model of Weak Pion Production Reactions

    Sato, T; Lee, T S H


    The dynamical model of pion electroproduction has been extended to investigate the weak pion production reactions. The predicted cross sections of neutrino-induced pion production reactions are in good agreement with the existing data. We show that the renormalized(dressed) axial N-$\\Delta$ form factor contains large dynamical pion cloud effects and this renormalization effects are crucial in getting agreement with the data. We conclude that the N-$\\Delta$ transitions predicted by the constituent quark model are consistent with the existing neutrino induced pion production data in the $\\Delta$ region.

  5. Ab initio path-integral calculations of kinetic and equilibrium isotope effects on base-catalyzed RNA transphosphorylation models.

    Wong, Kin-Yiu; Xu, Yuqing; York, Darrin M


    Detailed understandings of the reaction mechanisms of RNA catalysis in various environments can have profound importance for many applications, ranging from the design of new biotechnologies to the unraveling of the evolutionary origin of life. An integral step in the nucleolytic RNA catalysis is self-cleavage of RNA strands by 2'-O-transphosphorylation. Key to elucidating a reaction mechanism is determining the molecular structure and bonding characteristics of transition state. A direct and powerful probe of transition state is measuring isotope effects on biochemical reactions, particularly if we can reproduce isotope effect values from quantum calculations. This article significantly extends the scope of our previous joint experimental and theoretical work in examining isotope effects on enzymatic and nonenzymatic 2'-O-transphosphorylation reaction models that mimic reactions catalyzed by RNA enzymes (ribozymes), and protein enzymes such as ribonuclease A (RNase A). Native reactions are studied, as well as reactions with thio substitutions representing chemical modifications often used in experiments to probe mechanism. Here, we report and compare results from eight levels of electronic-structure calculations for constructing the potential energy surfaces in kinetic and equilibrium isotope effects (KIE and EIE) computations, including a "gold-standard" coupled-cluster level of theory [CCSD(T)]. In addition to the widely used Bigeleisen equation for estimating KIE and EIE values, internuclear anharmonicity and quantum tunneling effects were also computed using our recently developed ab initio path-integral method, that is, automated integration-free path-integral method. The results of this work establish an important set of benchmarks that serve to guide calculations of KIE and EIE for RNA catalysis. Copyright © 2014 Wiley Periodicals, Inc.

  6. QGSM development for spallation reactions modeling

    Gudima K.K.


    Full Text Available The growing interest in spallation neutron sources, accelerator-driven systems, R&D of rare isotope beams, and development of external beam radiation therapy necessitated the improvement of nuclear reaction models for both stand-alone codes for the analysis of nuclear reactions and event generators within the Monte Carlo transport systems for calculations of interactions of high-energy particles with matter in a wide range of energy and in arbitrary 3D geometry of multicomponent targets. The exclusive approach to the description of nuclear reactions is the most effective for detailed calculation of inelastic interactions with atomic nuclei. It provides the correct description of particle production, single- and double-differential spectra, recoil, and fission product yields. This approach has been realized in the Quark Gluon String Model (QGSM for nuclear reactions induced by photons, hadrons, and high energy heavy ions. In this article, improved versions of the QGSM model and a corresponding code have been developed tested and bench marked against experimental data for neutron production in spallation reactions on thin and thick targets in the energy range from a few MeV to several GeV/nucleon.

  7. QGSM development for spallation reactions modeling

    Baznat, M. I.; Chigrinov, S. E.; Gudima, K. K.


    The growing interest in spallation neutron sources, accelerator-driven systems, R&D of rare isotope beams, and development of external beam radiation therapy necessitated the improvement of nuclear reaction models for both stand-alone codes for the analysis of nuclear reactions and event generators within the Monte Carlo transport systems for calculations of interactions of high-energy particles with matter in a wide range of energy and in arbitrary 3D geometry of multicomponent targets. The exclusive approach to the description of nuclear reactions is the most effective for detailed calculation of inelastic interactions with atomic nuclei. It provides the correct description of particle production, single- and double-differential spectra, recoil, and fission product yields. This approach has been realized in the Quark Gluon String Model (QGSM) for nuclear reactions induced by photons, hadrons, and high energy heavy ions. In this article, improved versions of the QGSM model and a corresponding code have been developed tested and bench marked against experimental data for neutron production in spallation reactions on thin and thick targets in the energy range from a few MeV to several GeV/nucleon.

  8. Effect of low and high heating rates on reaction path of Ni(V)/Al multilayer

    Maj, Łukasz, E-mail: [Institute of Metallurgy and Materials Science, Polish Academy of Sciences, 25 Reymonta St., 30-059 Kraków (Poland); Morgiel, Jerzy; Szlezynger, Maciej [Institute of Metallurgy and Materials Science, Polish Academy of Sciences, 25 Reymonta St., 30-059 Kraków (Poland); Bała, Piotr; Cios, Grzegorz [AGH University of Science and Technology, Academic Centre for Materials and Nanotechnology, 30 Kawiory St., 30-055 Kraków (Poland)


    The effect of heating rates of Ni(V)/Al NanoFoils{sup ®} was investigated with transmission electron microscopy (TEM). The Ni(V)/Al were subjected to heating by using differential scanning calorimetry (DSC), in-situ TEM or electric pulse. Local chemical analysis was carried out using energy dispersive X-ray spectroscopy (EDS). Phase analysis was done with X-ray diffractions (XRD) and selected area electron diffractions (SAED). The experiments showed that slow heating in DSC results in development of separate exothermic effects at ∼230 °C, ∼280 °C and ∼390 °C, corresponding to precipitation of Al{sub 3}Ni, Al{sub 3}Ni{sub 2} and NiAl phases, respectively, i.e. like in vanadium free Ni/Al multilayers. Further heating to 700 °C allowed to obtain a single phase NiAl foil. The average grain size (g.s.) of NiAl phase produced in the DSC heat treated foil was comparable with the Ni(V)/Al multilayer period (∼50 nm), whereas in the case of reaction initiated with electric pulse the g.s. was in the micrometer range. Upon slow heating vanadium tends to segregate to zones parallel to the original multilayer internal interfaces, while in SHS process vanadium-rich phases precipitates at grain boundaries of the NiAl phase. - Highlights: • Peaks in DSC heating of Ni(V)/Al were explained by in-situ TEM observations. • Nucleation of Al{sub 3}Ni, Al{sub 3}Ni{sub 2} and NiAl at slow heating of Ni(V)/Al was documented. • Near surface NiAl obtained from NanoFoil show Ag precipitates at grain boundaries.

  9. Path Optimization for Single and Multiple Searchers: Models and Algorithms


    in that cell during that time period given the target occupies cell c at time period t is described as 1− exp(−αc, tyc ,t) instead of 1− (1−g(c, t))yc,t...yc,t number of searchers in cell c in time period t Formulation min f(y) = ∑ ω∈Ω pω exp  −∑ c,t αωc, tyc ,t   s.t.∑ c′∈R(c) xc′,c,t−1 = ∑ c′∈F(c) xc...are ∂f(y) ∂yc,t = − ∑ ω∈Ω pωα ω c,t exp(− ∑ c,t αωc, tyc ,t). (IV.1) Since the formulation uses all possible target paths ω ∈ Ω, if the number of

  10. Mathematical model for path selection by ants between nest and food source.

    Bodnar, Marek; Okińczyc, Natalia; Vela-Pérez, M


    Several models have been proposed to describe the behavior of ants when moving from nest to food sources. Most of these studies where based on numerical simulations with no mathematical justification. In this paper, we propose a mechanism for the formation of paths of minimal length between two points by a collection of individuals undergoing reinforced random walks taking into account not only the lengths of the paths but also the angles (connected to the preference of ants to move along straight lines). Our model involves reinforcement (pheromone accumulation), persistence (tendency to preferably follow straight directions in absence of any external effect) and takes into account the bifurcation angles of each edge (represented by a probability of willingness of choosing the path with the smallest angle). We describe analytically the results for 2 ants and different path lengths and numerical simulations for several ants. Copyright © 2016 Elsevier Inc. All rights reserved.

  11. DSMC modeling of flows with recombination reactions

    Gimelshein, Sergey; Wysong, Ingrid


    An empirical microscopic recombination model is developed for the direct simulation Monte Carlo method that complements the extended weak vibrational bias model of dissociation. The model maintains the correct equilibrium reaction constant in a wide range of temperatures by using the collision theory to enforce the number of recombination events. It also strictly follows the detailed balance requirement for equilibrium gas. The model and its implementation are verified with oxygen and nitrogen heat bath relaxation and compared with available experimental data on atomic oxygen recombination in argon and molecular nitrogen.

  12. Reaction-diffusion pulses: a combustion model

    Campos, Daniel [Grup de FIsica EstadIstica, Dept. de FIsica, Universitat Autonoma de Barcelona, E-08193 Bellaterrra (Spain); Llebot, Josep Enric [Grup de FIsica EstadIstica, Dept. de FIsica, Universitat Autonoma de Barcelona, E-08193 Bellaterrra (Spain); Fort, Joaquim [Dept. de FIsica, Univ. de Girona, Campus de Montilivi, 17071 Girona, Catalonia (Spain)


    We focus on a reaction-diffusion approach proposed recently for experiments on combustion processes, where the heat released by combustion follows first-order reaction kinetics. This case allows us to perform an exhaustive analytical study. Specifically, we obtain the exact expressions for the speed of the thermal pulses, their maximum temperature and the condition of self-sustenance. Finally, we propose two generalizations of the model, namely, the case of several reactants burning together, and that of time-delayed heat conduction. We find an excellent agreement between our analytical results and simulations.

  13. Reaction Wheel Disturbance Model Extraction Software - RWDMES

    Blaurock, Carl


    The RWDMES is a tool for modeling the disturbances imparted on spacecraft by spinning reaction wheels. Reaction wheels are usually the largest disturbance source on a precision pointing spacecraft, and can be the dominating source of pointing error. Accurate knowledge of the disturbance environment is critical to accurate prediction of the pointing performance. In the past, it has been difficult to extract an accurate wheel disturbance model since the forcing mechanisms are difficult to model physically, and the forcing amplitudes are filtered by the dynamics of the reaction wheel. RWDMES captures the wheel-induced disturbances using a hybrid physical/empirical model that is extracted directly from measured forcing data. The empirical models capture the tonal forces that occur at harmonics of the spin rate, and the broadband forces that arise from random effects. The empirical forcing functions are filtered by a physical model of the wheel structure that includes spin-rate-dependent moments (gyroscopic terms). The resulting hybrid model creates a highly accurate prediction of wheel-induced forces. It accounts for variation in disturbance frequency, as well as the shifts in structural amplification by the whirl modes, as the spin rate changes. This software provides a point-and-click environment for producing accurate models with minimal user effort. Where conventional approaches may take weeks to produce a model of variable quality, RWDMES can create a demonstrably high accuracy model in two hours. The software consists of a graphical user interface (GUI) that enables the user to specify all analysis parameters, to evaluate analysis results and to iteratively refine the model. Underlying algorithms automatically extract disturbance harmonics, initialize and tune harmonic models, and initialize and tune broadband noise models. The component steps are described in the RWDMES user s guide and include: converting time domain data to waterfall PSDs (power spectral

  14. New Path for Building Compliance in ASHRAE Model Energy Efficiency Standard

    Rosenberg, Michael I.


    This article describes a new path for performance based compliance with ASHRAE Standard 90.1. Using Appendix G, the Performance Rating Method, this path allows the same simulated baseline model to be used for both code compliance and beyond code programs. The baseline is fixed at approximately 90.1-2004 and independent of the designer's chosen design solutions to the greatest extent possible

  15. A Reaction-Based River/Stream Water Quality Model: Reaction Network Decomposition and Model Application

    Fan Zhang


    Full Text Available This paper describes details of an automatic matrix decomposition approach for a reaction-based stream water quality model. The method yields a set of equilibrium equations, a set of kinetic-variable transport equations involving kinetic reactions only, and a set of component transport equations involving no reactions. Partial decomposition of the system of water quality constituent transport equations is performed via Gauss-Jordan column reduction of the reaction network by pivoting on equilibrium reactions to decouple equilibrium and kinetic reactions. This approach minimizes the number of partial differential advective-dispersive transport equations and enables robust numerical integration. Complete matrix decomposition by further pivoting on linearly independent kinetic reactions allows some rate equations to be formulated individually and explicitly enforces conservation of component species when component transport equations are solved. The methodology is demonstrated for a case study involving eutrophication reactions in the Des Moines River in Iowa, USA and for two hypothetical examples to illustrate the ability of the model to simulate sediment and chemical transport with both mobile and immobile water phases and with complex reaction networks involving both kinetic and equilibrium reactions.

  16. Investigation and Modelling of Diesel Hydrotreating Reactions

    Boesen, Rasmus Risum

    This project consists of a series of studies, that are related to hydrotreating of diesel. Hy- drotreating is an important refinery process, in which the oil stream is upgraded to meet the required environmental specifications and physical properties. Although hydrotreating is a ma- ture technology...... on a commercial CoMo catalyst, and a simple kinetic model is presented. Hydrogenation of fused aromatic rings are known to be fast, and it is possible, that the reaction rates are limited by either internal or external mass transfer. An experiment conducted at industrial temperatures and pressure, using...... kinetic models. Hydrogenation reactions are quite fast, and in order to avoid mass transfer limitations, and only measure intrinsic rates, experiments are often conducted, at conditions that are milder than in industrial units. A reactor model for a Robinson-Mahoney reactor that takes mass transfer...

  17. Structural Fluctuations in Enzyme-Catalyzed Reactions: Determinants of Reactivity in Fatty Acid Amide Hydrolase from Multivariate Statistical Analysis of Quantum Mechanics/Molecular Mechanics Paths.

    Lodola, Alessio; Sirirak, Jitnapa; Fey, Natalie; Rivara, Silvia; Mor, Marco; Mulholland, Adrian J


    The effects of structural fluctuations, due to protein dynamics, on enzyme activity are at the heart of current debates on enzyme catalysis. There is evidence that fatty acid amide hydrolase (FAAH) is an enzyme for which reaction proceeds via a high-energy, reactive conformation, distinct from the predominant enzyme-substrate complex (Lodola et al. Biophys. J. 2007, 92, L20-22). Identifying the structural causes of differences in reactivity between conformations in such complex systems is not trivial. Here, we show that multivariate analysis of key structural parameters can identify structural determinants of barrier height by analysis of multiple reaction paths. We apply a well-tested quantum mechanics/molecular mechanics (QM/MM) method to the first step of the acylation reaction between FAAH and oleamide substrate for 36 different starting structures. Geometrical parameters (consisting of the key bond distances that change during the reaction) were collected and used for principal component analysis (PCA), partial least-squares (PLS) regression analysis, and multiple linear regression (MLR) analysis. PCA indicates that different "families" of enzyme-substrate conformations arise from QM/MM molecular dynamics simulation and that rarely sampled, catalytically significant conformational states can be identified. PLS and MLR analyses allowed the construction of linear regression models, correlating the calculated activation barriers with simple geometrical descriptors. These analyses reveal the presence of two fully independent geometrical effects, explaining 78% of the variation in the activation barrier, which are directly correlated with transition-state stabilization (playing a major role in catalysis) and substrate binding. These results highlight the power of statistical approaches of this type in identifying crucial structural features that contribute to enzyme reactivity.

  18. A Local Search Modeling for Constrained Optimum Paths Problems (Extended Abstract

    Quang Dung Pham


    Full Text Available Constrained Optimum Path (COP problems appear in many real-life applications, especially on communication networks. Some of these problems have been considered and solved by specific techniques which are usually difficult to extend. In this paper, we introduce a novel local search modeling for solving some COPs by local search. The modeling features the compositionality, modularity, reuse and strengthens the benefits of Constrained-Based Local Search. We also apply the modeling to the edge-disjoint paths problem (EDP. We show that side constraints can easily be added in the model. Computational results show the significance of the approach.

  19. Ab initio study on the paths of oxygen abstraction of hydrogen trioxide (HO3) molecule in the HO3 + SO2 reaction

    R Bagherzadeh; Sattar Ebrahimi; Moein Goodarzi


    The reaction paths of hydrogen trioxide (HO3) with sulphur dioxide (SO2) have been investigated on the doublet potential energy surface, theoretically. All species of the title reaction have been optimized at the PMP2(FC)/cc-pVDZ computational level. Energetic data have been obtained at the CCSD(T)//PMP2 level employing the cc-pVDZ basis set. No stable collision complexes have been found between the SO2 and HO3 molecules. Therefore, the SO2 + HO3 reaction starts without initial associations. The four possible paths, P1 through P4, have been obtained for the formation of SO3 (D3h) + HOO$^{\\bullet}$ product. Our results show that these four paths include relatively high energy barriers to produce the final product of the SO3 (D3h) + HOO$^{\\bullet}$. Therefore, the SO2 + HO3 → SO3(D3h) + HOO$^{\\bullet}$ reaction is difficult to perform under atmospheric conditions. This means that the importance of SO2 + HO3 → SO3 (D3h) + HOO$^{\\bullet}$ reaction increases with increasing temperature and, this reaction plays an important role in the SO3(D3h) production as the main molecule of the formation of acid rain at high temperatures.

  20. Propagation Path Loss Models for 5G Urban Micro- and Macro-Cellular Scenarios

    Sun, Shu; Rappaport, Theodore S.; Rangan, Sundeep


    This paper presents and compares two candidate large-scale propagation path loss models, the alpha-beta-gamma (ABG) model and the close-in (CI) free space reference distance model, for the design of fifth generation (5G) wireless communication systems in urban micro- and macro-cellular scenarios....

  1. Women's Path into Science and Engineering Majors: A Structural Equation Model

    Camp, Amanda G.; Gilleland, Diane; Pearson, Carolyn; Vander Putten, Jim


    The intent of this study was to investigate the adequacy of Weidman's (1985, 1989) theoretical undergraduate socialization model as an empirical-based causal model pertaining to women's career path choice into a science or engineering (SE) major via structural equation modeling. Data were obtained from the Beginning Postsecondary Students…

  2. Kinematic modeling and path planning for MIRADAS arms

    Sabater, Josep; Gómez, José María.; López, Manuel; Torra, Jordi; Raines, Steven N.; Eikenberry, Stephen S.


    The Mid-resolution InfRAreD Astronomical Spectrograph (MIRADAS) is a near-infrared (NIR) multi-object spectrograph for the Gran Telescopio Canarias (GTC). It can simultaneously observe multiple targets selected by 20 identical deployable probe arms with pickoff mirror optics. The bases of the arms are fixed to the multiplexing system (MXS) plate, a circular platform, and arranged in a circular layout with minimum separation between elements of the arms. This document presents the MXS prototype P2a, a full-scale, fully operational prototype of a MIRADAS probe arm. This planar closed-loop mechanism compared to other previous designs offers some advantages specially in terms of stability and from the point of view of optics. Unfortunately, these benefits come at the expense of a more complicated kinematics and an unintuitive arm motion. Furthermore, the cryogenic motor controllers used in prototyping impose severe restrictions in path planing. They negatively impact in the slice of pie approach, a collision-avoidance patrolling strategy that can gives good results in other scenarios. This study is a starting point to define collision-free trajectory algorithms for the 20 probe arms of MIRADAS.

  3. Modeling shortest path selection of the ant Linepithema humile using psychophysical theory and realistic parameter values.

    von Thienen, Wolfhard; Metzler, Dirk; Witte, Volker


    The emergence of self-organizing behavior in ants has been modeled in various theoretical approaches in the past decades. One model explains experimental observations in which Argentine ants (Linepithema humile) selected the shorter of two alternative paths from their nest to a food source (shortest path experiments). This model serves as an important example for the emergence of collective behavior and self-organization in biological systems. In addition, it inspired the development of computer algorithms for optimization problems called ant colony optimization (ACO). In the model, a choice function describing how ants react to different pheromone concentrations is fundamental. However, the parameters of the choice function were not deduced experimentally but freely adapted so that the model fitted the observations of the shortest path experiments. Thus, important knowledge was lacking about crucial model assumptions. A recent study on the Argentine ant provided this information by measuring the response of the ants to varying pheromone concentrations. In said study, the above mentioned choice function was fitted to the experimental data and its parameters were deduced. In addition, a psychometric function was fitted to the data and its parameters deduced. Based on these findings, it is possible to test the shortest path model by applying realistic parameter values. Here we present the results of such tests using Monte Carlo simulations of shortest path experiments with Argentine ants. We compare the choice function and the psychometric function, both with parameter values deduced from the above-mentioned experiments. Our results show that by applying the psychometric function, the shortest path experiments can be explained satisfactorily by the model. The study represents the first example of how psychophysical theory can be used to understand and model collective foraging behavior of ants based on trail pheromones. These findings may be important for other

  4. Multiple Damage Progression Paths in Model-based Prognostics

    National Aeronautics and Space Administration — Model-based prognostics approaches employ do- main knowledge about a system, its components, and how they fail through the use of physics-based models. Compo- nent...


    Friedlander, E.M.; Gimpel, R.W.; Heckman, H.H.; Karant, Y.J.; Judek, B.; Ganssauge, E.


    We present in detail the description and the analysis of two independent experiments using Bevalac beams of {sup 16}O and {sup 56}Fe. From their results it is concluded that the reaction mean free paths of relativistic projectile fragments, 3 {<=} Z {<=} 26, are shorter for a few centimeters after emission than at large distances where they are compatible with values predicted from experiments on beam nuclei. The probability that this effect is due to a statistical fluctuation is <10{sup -3}. The effect is enhanced in later generations of fragments, the correlation between successive generations suggesting a kind of "memory" for the anomaly. Various systematic and spurious effects as well as conventional explanations are discussed mainly on the basis of direct experimental observations internal to our data, and found not to explain our results. The data can be interpreted by the relatively rare occurrence of anomalous fragments that interact with an unexpectedly large cross section. The statistical methods used in the analysis of the observations are fully described.

  6. NLOS UV Channel Modeling Using Numerical Integration and an Approximate Closed-Form Path Loss Model

    Gupta, Ankit; Brandt-Pearce, Maïté


    In this paper we propose a simulation method using numerical integration, and develop a closed-form link loss model for physical layer channel characterization for non-line of sight (NLOS) ultraviolet (UV) communication systems. The impulse response of the channel is calculated by assuming both uniform and Gaussian profiles for transmitted beams and different geometries. The results are compared with previously published results. The accuracy of the integration approach is compared to the Monte Carlo simulation. Then the path loss using the simulation method and the suggested closed-form expression are presented for different link geometries. The accuracies are evaluated and compared to the results obtained using other methods.

  7. Computer-Aided Modelling of Short-Path Evaporation for Chemical Product Purification, Analysis and Design

    Sales-Cruz, Alfonso Mauricio; Gani, Rafiqul


    An important stage in the design process for many chemical products is its manufacture where, for a class of chemical products that may be thermally unstable (such as, drugs, insecticides, flavours /fragrances, and so on), the purification step plays a major role. Short-path evaporation is a safe...... method, suitable for separation and purification of thermally unstable materials whose design and analysis can be efficiently performed through reliable model-based techniques. This paper presents a generalized model for short-path evaporation and highlights its development, implementation and solution...... glycerol, mono-, di- and triglycerides, and (b) the recovery of a pharmaceutical product from a six-component mixture. Validation of the short-path evaporation model is highlighted through the comparison of experimental data from an industrial pilot plant with the simulated results from the model. Also...

  8. Continuous Estimation of Wrist Torque from Surface EMG Signals Using Path-dependent Model

    PAN Li-zhi; ZHANG Ding-guo; SHENG Xin-jun; ZHU Xiang-yang


    Continuous estimation of wrist torque from surface electromyography (EMG) signals has been studied by some research institutes. Hysteresis effect is a phenomenon in EMG force relationship. In this work, a path-dependent model based on hysteresis effect was used for continuously estimating wrist torque from surface EMG signals. The surface EMG signals of the flexor carpi ulnaris (FCU) and extensor carpi radialis (ECR) were collected along with wrist torque of flexion/extension degree-of-freedom. EMG signal of FCU was used to estimate the torque of wrist flexion and EMG signal of ECR to estimate the torque of wrist extension. The existence of hysteresis effect has been proven either during wrist flexion or extension on all subjects. And the estimation performance of path-dependent model is much better than the overall model. Thus, the path-dependent model is suitable to improve the wrist torque's estimation accuracy.

  9. An Empirical Path-Loss Model for Wireless Channels in Indoor Short-Range Office Environment

    Ye Wang


    Full Text Available A novel empirical path-loss model for wireless indoor short-range office environment at 4.3–7.3 GHz band is presented. The model is developed based on the experimental datum sampled in 30 office rooms in both line of sight (LOS and non-LOS (NLOS scenarios. The model is characterized as the path loss to distance with a Gaussian random variable X due to the shadow fading by using linear regression. The path-loss exponent n is fitted by the frequency using power function and modeled as a frequency-dependent Gaussian variable as the standard deviation σ of X. The presented works should be available for the research of wireless channel characteristics under universal indoor short-distance environments in the Internet of Things (IOT.

  10. Path Loss Channel Model for Inland River Radio Propagation at 1.4 GHz

    Junyi Yu


    Full Text Available In this paper, a propagation path loss model for inland river is proposed by three improvements compared with the Round Earth Loss (REL model for open-sea environment. Specifically, parameters optimization uses Okumura-Hata model in dB scale to replace the equation transformed from the free space loss in REL model; secondly, diffraction loss caused by the obstacles (e.g., large buildings, bridges, or some other facilities near the river bank is also taken into account; mixed-path methodology as another improvement is used for Inland River (IR model because the actual propagation environment between transmitter (TX antenna and receiver (RX antenna contains both land part and water part. The paper presents a set of 1.4 GHz measurements conducted along the Yangtze River in Wuhan. According to the comparison between path loss models and experimental results, IR model shows a good matching degree. After that, Root Mean Square Error (RMSE, Grey Relation Grade and Mean Absolute Percentage Error (GRG-MAPE, Pearson Correlation Coefficient, and Mean Absolute Percentage Error (PCC-MAPE are employed to implement quantitative analysis. The results prove that IR model with consideration of mixed path and deterministic information is more accurate than other classic empirical propagation models for these scenarios.

  11. Progressive collapse analysis using updated models for alternate path analysis after a blast

    Eskew, Edward; Jang, Shinae; Bertolaccini, Kelly


    Progressive collapse is of rising importance within the structural engineering community due to several recent cases. The alternate path method is a design technique to determine the ability of a structure to sustain the loss of a critical element, or elements, and still resist progressive collapse. However, the alternate path method only considers the removal of the critical elements. In the event of a blast, significant damage may occur to nearby members not included in the alternate path design scenarios. To achieve an accurate assessment of the current condition of the structure after a blast or other extreme event, it may be necessary to reduce the strength or remove additional elements beyond the critical members designated in the alternate path design method. In this paper, a rapid model updating technique utilizing vibration measurements is used to update the structural model to represent the real-time condition of the structure after a blast occurs. Based upon the updated model, damaged elements will either have their strength reduced, or will be removed from the simulation. The alternate path analysis will then be performed, but only utilizing the updated structural model instead of numerous scenarios. After the analysis, the simulated response from the analysis will be compared to failure conditions to determine the buildings post-event condition. This method has the ability to incorporate damage to noncritical members into the analysis. This paper will utilize numerical simulations based upon a unified facilities criteria (UFC) example structure subjected to an equivalent blast to validate the methodology.

  12. IIR filtering based adaptive active vibration control methodology with online secondary path modeling using PZT actuators

    Boz, Utku; Basdogan, Ipek


    Structural vibrations is a major cause for noise problems, discomfort and mechanical failures in aerospace, automotive and marine systems, which are mainly composed of plate-like structures. In order to reduce structural vibrations on these structures, active vibration control (AVC) is an effective approach. Adaptive filtering methodologies are preferred in AVC due to their ability to adjust themselves for varying dynamics of the structure during the operation. The filtered-X LMS (FXLMS) algorithm is a simple adaptive filtering algorithm widely implemented in active control applications. Proper implementation of FXLMS requires availability of a reference signal to mimic the disturbance and model of the dynamics between the control actuator and the error sensor, namely the secondary path. However, the controller output could interfere with the reference signal and the secondary path dynamics may change during the operation. This interference problem can be resolved by using an infinite impulse response (IIR) filter which considers feedback of the one or more previous control signals to the controller output and the changing secondary path dynamics can be updated using an online modeling technique. In this paper, IIR filtering based filtered-U LMS (FULMS) controller is combined with online secondary path modeling algorithm to suppress the vibrations of a plate-like structure. The results are validated through numerical and experimental studies. The results show that the FULMS with online secondary path modeling approach has more vibration rejection capabilities with higher convergence rate than the FXLMS counterpart.

  13. A Path Model for Students' Attitudes to Writing a Thesis.

    Sachs, John


    Using responses of 90 undergraduate and graduate students, developed a model in which action-control belief variables have only an indirect effect on students' attitudes to writing a thesis mediated through two academic orientation variables. The model accounted for a large proportion of the repeatable variance in the two academic orientation…

  14. A Path Model for Students' Attitudes to Writing a Thesis.

    Sachs, John


    Using responses of 90 undergraduate and graduate students, developed a model in which action-control belief variables have only an indirect effect on students' attitudes to writing a thesis mediated through two academic orientation variables. The model accounted for a large proportion of the repeatable variance in the two academic orientation…

  15. Path Loss Prediction Over the Lunar Surface Utilizing a Modified Longley-Rice Irregular Terrain Model

    Foore, Larry; Ida, Nathan


    This study introduces the use of a modified Longley-Rice irregular terrain model and digital elevation data representative of an analogue lunar site for the prediction of RF path loss over the lunar surface. The results are validated by theoretical models and past Apollo studies. The model is used to approximate the path loss deviation from theoretical attenuation over a reflecting sphere. Analysis of the simulation results provides statistics on the fade depths for frequencies of interest, and correspondingly a method for determining the maximum range of communications for various coverage confidence intervals. Communication system engineers and mission planners are provided a link margin and path loss policy for communication frequencies of interest.

  16. Reaction-contingency based bipartite Boolean modelling


    Background Intracellular signalling systems are highly complex, rendering mathematical modelling of large signalling networks infeasible or impractical. Boolean modelling provides one feasible approach to whole-network modelling, but at the cost of dequantification and decontextualisation of activation. That is, these models cannot distinguish between different downstream roles played by the same component activated in different contexts. Results Here, we address this with a bipartite Boolean modelling approach. Briefly, we use a state oriented approach with separate update rules based on reactions and contingencies. This approach retains contextual activation information and distinguishes distinct signals passing through a single component. Furthermore, we integrate this approach in the rxncon framework to support automatic model generation and iterative model definition and validation. We benchmark this method with the previously mapped MAP kinase network in yeast, showing that minor adjustments suffice to produce a functional network description. Conclusions Taken together, we (i) present a bipartite Boolean modelling approach that retains contextual activation information, (ii) provide software support for automatic model generation, visualisation and simulation, and (iii) demonstrate its use for iterative model generation and validation. PMID:23835289

  17. A generalized recipe to construct elementary or multi-step reaction paths via a stochastic formulation: Application to the conformational change in noble gas clusters

    Talukder, Srijeeta; Sen, Shrabani [Department of Chemistry, University of Calcutta, 92 A P C Road, Kolkata 700 009 (India); Sharma, Rahul [Department of Chemistry, St. Xavier’s College, 30 Mother Teresa Sarani, Kolkata 700 016 (India); Banik, Suman K., E-mail: [Department of Chemistry, Bose Institute, 93/1 A P C Road, Kolkata 700 009 (India); Chaudhury, Pinaki, E-mail: [Department of Chemistry, University of Calcutta, 92 A P C Road, Kolkata 700 009 (India)


    Highlights: • We demonstrate a general strategy to map out reaction paths irrespective of the number of kinetic steps involved. • The objective function proposed does not need the information of gradient norm and eigenvalue of Hessian matrix explicitly. • A stochastic optimizer Simulated Annealing is used in searching reaction path. • The strategy is applied in mapping out the path for conformational changes in pure Ar clusters and Ar{sub N}Xe mixed clusters. - abstract: In this paper we demonstrate a general strategy to map out reaction paths irrespective of the number of kinetic steps required to bring about the change. i.e., whether the transformation takes place in a single step or in multiple steps with the appearance of intermediates. The objective function proposed is unique and works equally well for a concerted or a multiple step pathway. As the objective function proposed does not explicitly involves the calculation of the gradient of the potential energy function or the eigenvalues of the Hessian Matrix during the iterative process, the calculation is computationally economical. To map out the reaction path, we cast the entire problem as one of optimization and the solution is done with the use of the stochastic optimizer Simulated Annealing. The formalism is tested on Argon clusters (Ar{sub N}) and Argon clusters singly doped with Xenon (Ar{sub N-1}Xe). The size of the systems for which the method is applied ranges from N=7-25, where N is the total number of atoms in the cluster. We also test the results obtained by us by comparing with an established gradient only method. Moreover to demonstrate that our strategy can overcome the standard problems of drag method, we apply our strategy to a two dimensional LEPS + harmonic oscillator Potential to locate the TS, in which standard drag method has been seen to encounter problems.

  18. A Split-Path Schema-Based RFID Data Storage Model in Supply Chain Management

    Jianfeng Zhang


    Full Text Available In modern supply chain management systems, Radio Frequency IDentification (RFID technology has become an indispensable sensor technology and massive RFID data sets are expected to become commonplace. More and more space and time are needed to store and process such huge amounts of RFID data, and there is an increasing realization that the existing approaches cannot satisfy the requirements of RFID data management. In this paper, we present a split-path schema-based RFID data storage model. With a data separation mechanism, the massive RFID data produced in supply chain management systems can be stored and processed more efficiently. Then a tree structure-based path splitting approach is proposed to intelligently and automatically split the movement paths of products . Furthermore, based on the proposed new storage model, we design the relational schema to store the path information and time information of tags, and some typical query templates and SQL statements are defined. Finally, we conduct various experiments to measure the effect and performance of our model and demonstrate that it performs significantly better than the baseline approach in both the data expression and path-oriented RFID data query performance.

  19. A theoretical model of metal surface reactions

    Shustorovich, E. (Eastman Kodak Co., Rochester, NY); Baetzold, R.C.; Muetterties, E.L.


    Metal surface reactions are modeled with a novel theoretical construct in which periodic trends can be scrutinized. The theoretical model is succinctly presented and a conspectus of periodic trends, based on the model, is explored. Periodic trends are discussed in the contexts of chemisorption bond energies, electron transfer between metal surface and adsorbate, stereochemical features of chemisorption states for closed-shell diatomic and linear X-CN or X-NC molecules, and hydrocarbon reactions. Hydrocarbon C-H bond-breaking processes are analyzed in terms of d-level occupancy, electron transfer, and stereochemistry of intermediates. Conceptually and computationally, the metal surface is characterized as a good electron donor: antibonding molecular orbitals of the adsorbate species appear to be significant contributors to the chemisorption bond and also play a decisive role in bond-breaking processes. No aspect of the model projections is inconsistent with the experimental data although the electronic characterization of some chemisorption states are counter to commonly held perceptions.

  20. Standard Cost Model: Three Different Paths and their Common Problems

    Jacopo Torriti


    Full Text Available Red tape is not desirable as it impedes business growth. Relief from the administrative burdens that businesses face due to legislation can benefit the whole economy, especially at times of recession. However, recent governmental initiatives aimed at reducing administrative burdens have encountered some success, but also failures. This article compares three national initiatives – in the Netherlands, UK and Italy - aimed at cutting red tape by using the Standard Cost Model. Findings highlight the factors affecting the outcomes of measurement and reduction plans and ways to improve the Standard Cost Model methodology.

  1. Quantitative models of hydrothermal fluid-mineral reaction: The Ischia case

    Di Napoli, Rossella; Federico, Cinzia; Aiuppa, Alessandro; D'Antonio, Massimo; Valenza, Mariano


    The intricate pathways of fluid-mineral reactions occurring underneath active hydrothermal systems are explored in this study by applying reaction path modelling to the Ischia case study. Ischia Island, in Southern Italy, hosts a well-developed and structurally complex hydrothermal system which, because of its heterogeneity in chemical and physical properties, is an ideal test sites for evaluating potentialities/limitations of quantitative geochemical models of hydrothermal reactions. We used the EQ3/6 software package, version 7.2b, to model reaction of infiltrating waters (mixtures of meteoric water and seawater in variable proportions) with Ischia's reservoir rocks (the Mount Epomeo Green Tuff units; MEGT). The mineral assemblage and composition of such MEGT units were initially characterised by ad hoc designed optical microscopy and electron microprobe analysis, showing that phenocrysts (dominantly alkali-feldspars and plagioclase) are set in a pervasively altered (with abundant clay minerals and zeolites) groundmass. Reaction of infiltrating waters with MEGT minerals was simulated over a range of realistic (for Ischia) temperatures (95-260 °C) and CO2 fugacities (10-0.2 to 100.5) bar. During the model runs, a set of secondary minerals (selected based on independent information from alteration minerals' studies) was allowed to precipitate from model solutions, when saturation was achieved. The compositional evolution of model solutions obtained in the 95-260 °C runs were finally compared with compositions of Ischia's thermal groundwaters, demonstrating an overall agreement. Our simulations, in particular, well reproduce the Mg-depleting maturation path of hydrothermal solutions, and have end-of-run model solutions whose Na-K-Mg compositions well reflect attainment of full-equilibrium conditions at run temperature. High-temperature (180-260 °C) model runs are those best matching the Na-K-Mg compositions of Ischia's most chemically mature water samples

  2. Extended FEM modeling of crack paths near inclusions

    Nielsen, Chris Valentin; Legarth, Brian Nyvang; Niordson, Christian Frithiof


    The extended FEM is applied to model crack growth near inclusions. A procedure to handle different propagation rates at different crack tips is presented. The examples considered investigate uniform tension as well as equibiaxial tension under plane strain conditions. A parameter study analyzes...

  3. Violence in Young Adolescents' Relationships: A Path Model

    Josephson, Wendy L.; Proulx, Jocelyn B.


    A structural equation model based on social cognitive theory was used to predict relationship violence from young adolescents' knowledge, self-efficacy, attitudes, and alternative conflict strategies (n = 143 male and 147 female grade 7-9 students). A direct causal effect was supported for violence-tolerant attitudes and psychologically aggressive…

  4. Atomistic modeling of different loading paths in single crystal copper and aluminum

    R. Pezer


    Full Text Available Utilizing molecular dynamics (MD integration model we have investigated some of the relevant physical processes caused by different loading paths at the atomic level in Cu and Al monocrystal specimen. Interactions among the atoms in the bulk are modeled with the standard realistic Embedded Atom Method (EAM potentials. MD simulation gives us the detailed information about non-equilibrium dynamics including crystal structure defects, vacancies and dislocations. In particular, we have obtained result that indicate increase in the total energy of the crystal during loading (especially cyclic that provides us direct quantitative evidence of the metal weakening. For the basic response, we have deformed copper and aluminum single crystal according to the simple loading path and a series of multiaxial loading-paths including cyclic repetition. We compute equivalent stress-strain diagrams as well as dislocation total length vs time graphs to describe signatures of the anisotropic response of the crystal

  5. Balanced growth path solutions of a Boltzmann mean field game model for knowledge growth

    Burger, Martin


    In this paper we study balanced growth path solutions of a Boltzmann mean field game model proposed by Lucas and Moll [15] to model knowledge growth in an economy. Agents can either increase their knowledge level by exchanging ideas in learning events or by producing goods with the knowledge they already have. The existence of balanced growth path solutions implies exponential growth of the overall production in time. We prove existence of balanced growth path solutions if the initial distribution of individuals with respect to their knowledge level satisfies a Pareto-tail condition. Furthermore we give first insights into the existence of such solutions if in addition to production and knowledge exchange the knowledge level evolves by geometric Brownian motion.

  6. Guilty or not? A path model of women's sexual force fantasies.

    Shulman, Julie L; Horne, Sharon G


    This study estimated a path model of women's forceful sexual fantasies. Constructs examined were childhood sexual abuse, feminist beliefs, sexual guilt, erotophilia, and sexual experience. The study clarifies how these factors mediate one another in relationship to forceful sexual fantasies, and is first to examine the effects of feminist beliefs on forceful sexual fantasy. Adult women (N = 261) participated by completing an online survey. A path from sex guilt to forceful sexual fantasy, mediated by erotophilia, was found, wherein low levels of sex guilt and high levels of erotophilia were found to predict forceful sexual fantasy. A direct path between childhood sexual abuse and forceful sexual fantasy was also found. The resulting model is discussed in relation to previously-proposed theories on the role of force in women's sexual fantasies.

  7. Counterfactual Graphical Models for Mediation Analysis via Path-Specific Effects

    Shpitser, Ilya


    Potential outcome counterfactuals represent variation in the outcome of interest after a hypothetical treatment or intervention is performed. Causal graphical models are a concise, intuitive way of representing causal assumptions, including independence constraints among such counterfactuals. Much of modern causal inference is concerned with expressing cause effect relationships of interest in counterfactual form, showing how the resulting counterfactuals can be identified (that is expressed in terms of available data, using domain-specific causal assumptions), and subsequently estimated using statistical methods. In this paper we will use causal graphical models to analyze the identification problem of the so-called \\emph{path-specific effects}, that is effects of treatment on outcome along certain specified causal paths. Such effects arise in mediation analysis settings where it's important to distinguish direct and indirect effects of treatment. We review existing results on path-specific effects in the fu...

  8. Parallel Path Magnet Motor: Development of the Theoretical Model and Analysis of Experimental Results

    Dirba, I.; Kleperis, J.


    Analytical and numerical modelling is performed for the linear actuator of a parallel path magnet motor. In the model based on finite-element analysis, the 3D problem is reduced to a 2D problem, which is sufficiently precise in a design aspect and allows modelling the principle of a parallel path motor. The paper also describes a relevant numerical model and gives comparison with experimental results. The numerical model includes all geometrical and physical characteristics of the motor components. The magnetic flux density and magnetic force are simulated using FEMM 4.2 software. An experimental model has also been developed and verified for the core of switchable magnetic flux linear actuator and motor. The results of experiments are compared with those of theoretical/analytical and numerical modelling.

  9. Reaction-diffusion models of decontamination

    Hjorth, Poul G.

    A contaminant, which also contains a polymer is in the form of droplets on a solid surface. It is to be removed by the action of a decontaminant, which is applied in aqueous solution. The contaminant is only sparingly soluble in water, so the reaction mechanism is that it slowly dissolves...... in the aqueous solution and then is oxidized by the decontaminant. The polymer is insoluble in water, and so builds up near the interface, where its presence can impede the transport of contaminant. In these circumstances, Dstl wish to have mathematical models that give an understanding of the process, and can...

  10. Deparametrization and path integral quantization of cosmological models

    Simeone, Claudio


    The problem of time is a central feature of quantum cosmology: differing from ordinary quantum mechanics, in cosmology there is nothing "outside" the system which plays the role of clock, and this makes difficult the obtention of a consistent quantization. A possible solution is to assume that a subset of the variables describing the state of the universe can be a clock for the remaining of the system. Following this line, in this book a new proposal consisting in the previous identification of time by means of gauge fixation is applied to the quantization of homogeneous cosmological models. B

  11. Path Sensitization

    赵著行; 闵应骅; 等


    For different delay models,the concept of sensitization can be very different.Traditonal concepts of sensitization cannot precisely describe circuit behavior when the input vectors change very fast.Using Boolean process aporoach,this paper presents a new definition of sensitization for arbitrary input waveforms.By this new concept it is found that if the inputs of a combinational circuit can change at any time,and each gate's delay varies within an interval (bounded gate delay model),then every path,which is not necessarily a single topological path,is sensitizable.From the experimental results it can be seen that,all nonsensitizable paths for traditional concepts actually can propagate transitions along them for some input waveforms.However,specified time between input transitions(STBIT) and minimum permissible pulse width(ε)are two major factors to make some paths non-sensitizable.

  12. Disciplines, models, and computers: the path to computational quantum chemistry.

    Lenhard, Johannes


    Many disciplines and scientific fields have undergone a computational turn in the past several decades. This paper analyzes this sort of turn by investigating the case of computational quantum chemistry. The main claim is that the transformation from quantum to computational quantum chemistry involved changes in three dimensions. First, on the side of instrumentation, small computers and a networked infrastructure took over the lead from centralized mainframe architecture. Second, a new conception of computational modeling became feasible and assumed a crucial role. And third, the field of computa- tional quantum chemistry became organized in a market-like fashion and this market is much bigger than the number of quantum theory experts. These claims will be substantiated by an investigation of the so-called density functional theory (DFT), the arguably pivotal theory in the turn to computational quantum chemistry around 1990.

  13. Simulation of system models containing zero-order causal paths - I. Classification of zero-order causal paths

    Dijk, van, Nico M.; Breedveld, P.C.


    The existence of zero-order causal paths in bond graphs of physical systems implies the set of state equations to be an implicit mixed set of Differential and Algebraic Equations (DAEs). In the block diagram expansion of such a bond graph, this type of causal path corresponds with a zero-order loop. In this paper the numerical solution of the DAEs by methods commonly used for solving stiff systems of Ordinary Differential Equations (ODEs) is discussed. Apart from a description of the numerica...

  14. Multigroup Analysis in Partial Least Squares (PLS) Path Modeling: Alternative Methods and Empirical Results

    Sarstedt, Marko; Henseler, Jörg; Ringle, Christian M.


    Purpose – Partial least squares (PLS) path modeling has become a pivotal empirical research method in international marketing. Owing to group comparisons' important role in research on international marketing, we provide researchers with recommendations on how to conduct multigroup analyses in PLS p

  15. The use of partial least squares path modeling in international marketing

    Henseler, Jörg; Ringle, Christian M.; Sinkovics, Rudolf R.


    In order to determine the status quo of PLS path modeling in international marketing research, we conducted an exhaustive literature review. An evaluation of double-blind reviewed journals through important academic publishing databases (e.g., ABI/Inform, Elsevier ScienceDirect, Emerald Insight, Goo

  16. Factors Affecting Technology Integration in K-12 Classrooms: A Path Model

    Inan, Fethi A.; Lowther, Deborah L.


    The purpose of this study was to examine the direct and indirect effects of teachers' individual characteristics and perceptions of environmental factors that influence their technology integration in the classroom. A research-based path model was developed to explain causal relationships between these factors and was tested based on data gathered…

  17. The use of partial least squares path modeling in international marketing

    Henseler, Jörg; Ringle, Christian M.; Sinkovics, Rudolf R.


    In order to determine the status quo of PLS path modeling in international marketing research, we conducted an exhaustive literature review. An evaluation of double-blind reviewed journals through important academic publishing databases (e.g., ABI/Inform, Elsevier ScienceDirect, Emerald Insight,

  18. Non-smooth environment modeling and global path planning for mobile robots

    邹小兵; 蔡自兴; 孙国荣


    An Approximate Voronoi Boundary Network is constructed as the environmental model by way of enlar-ging the obstacle raster. The connectivity of the path network under complex environment is ensured through build-ing the second order Approximate Voronoi Boundary Network after adding virtual obstacles at joint-close grids. Thismethod embodies the network structure of the free area of environment with less nodes, so the complexity of pathplanning problem is reduced largely. An optimized path for mobile robot under complex environment is obtainedthrough the Genetic Algorithm based on the elitist rule and re-optimized by using the path-tightening method. Sincethe elitist one has the only authority of crossover, the management of one group becomes simple, which makes forobtaining the optimized path quickly. The Approximate Voronoi Boundary Network has a good tolerance to the im-precise a priori information and the noises of sensors under complex environment. Especially it is robust in dealingwith the local or partial changes, so a small quantity of dynamic obstacles is difficult to alter the overall character ofits connectivity, which means that it can also be adopted in dynamic environment by fusing the local path planning.

  19. Modeling stochasticity in biochemical reaction networks

    Constantino, P. H.; Vlysidis, M.; Smadbeck, P.; Kaznessis, Y. N.


    Small biomolecular systems are inherently stochastic. Indeed, fluctuations of molecular species are substantial in living organisms and may result in significant variation in cellular phenotypes. The chemical master equation (CME) is the most detailed mathematical model that can describe stochastic behaviors. However, because of its complexity the CME has been solved for only few, very small reaction networks. As a result, the contribution of CME-based approaches to biology has been very limited. In this review we discuss the approach of solving CME by a set of differential equations of probability moments, called moment equations. We present different approaches to produce and to solve these equations, emphasizing the use of factorial moments and the zero information entropy closure scheme. We also provide information on the stability analysis of stochastic systems. Finally, we speculate on the utility of CME-based modeling formalisms, especially in the context of synthetic biology efforts.

  20. Microscopic model for chemical etchability along radiation damage paths in solids

    Mukhtar Ahmed RANA


    It would be very interesting to develop a picture about removal of atoms from the radiation damaged paths or latent nuclear tracks and undamaged bulk material in track detectors. Here, theory of chemical etching is described briefly and a new model for chemical etching along radiation damaged paths in solids is developed based on basic scientific facts and valid assumptions. Dependence of chemical etching on radiation damage intensity and etching conditions is discussed. A new parameter for etching along radiation damaged paths is introduced, which is useful for investigation of relationship between chemical etchability and radiation damage in a solid. Results and discussion presented here are also useful for further development of nuclear waste immobilization.

  1. Path Generation for High-Performance Motion of ROVs Based on a Reference Model

    Daniel de A. Fernandes


    Full Text Available This paper deals with the generation of sufficiently smooth position, velocity, and acceleration references for guiding the motion of an ROV along purposefully defined curvature-continuous paths in automated missions. The references are meant to be employed in high-performance trajectory tracking and dynamic positioning applications. The path planning problem is not in the scope of this work. A reference model that synthesises references concerning a single Degree-of-Freedom (DoF motion is initially described. Then, the use of the synthesised references as the parametrisation for other references concerning multiple DoF motion along curvature-continuous paths is exploited. Results from computer simulations and full-scale sea trials, both based on the NTNU's ROV Minerva, are presented and discussed.

  2. Model for the Path Loss of In-room Reverberant Channels

    Steinböck, Gerhard; Pedersen, Troels; Fleury, Bernard Henri


    A general path loss model for in-room radio channels is proposed. The model is based on experimental observations of the behavior of the delay power spectrum in closed rooms. In a given closed room, the early part of the spectrum observed at different positions typically consists of a dominant...... allows for the prediction of path loss, mean delay, and RMS delay spread versus distance. We use measurements to validate the proposed model and we observe good agreement of the model prediction for mean delay and RMS delay spread....... component (peak) that vanishes as the transmitter-receiver distance increases, while the late part decays versus distance according to the same exponential law regardless of this distance. These observations motivate the proposed model of the delay power spectrum with an early dominant component...

  3. Comparative Analysis of Empirical Path Loss Model for Cellular Transmission in Rivers State

    B.O.H Akinwole, Biebuma J.J


    Full Text Available This paper presents a comparative analysis of three empirical path loss models with measured data for urban, suburban, and rural areas in Rivers State. The three models investigated were COST 231 Hata, SUI,ECC-33models. A downlink data was collected at operating frequency of 2100MHz using drive test procedure consisting of test mobile phones to determine the received signal power (RSCP at specified receiver distanceson a Globacom Node Bs located in some locations in the State. This test was carried out for investigating the effectiveness of the commonly used existing models for Cellular transmission. The results analysed were based on Mean Square Error (MSE and Standard Deviation (SD and were simulated on MATLAB (7.5.0. The results show that COST 231 Hata model gives better predictions and therefore recommended for path loss predictions in River State.

  4. The aggregate path coupling method for the Potts model on bipartite graph

    Hernández, José C.; Kovchegov, Yevgeniy; Otto, Peter T.


    In this paper, we derive the large deviation principle for the Potts model on the complete bipartite graph Kn,n as n increases to infinity. Next, for the Potts model on Kn,n, we provide an extension of the method of aggregate path coupling that was originally developed in the work of Kovchegov, Otto, and Titus [J. Stat. Phys. 144(5), 1009-1027 (2011)] for the mean-field Blume-Capel model and in Kovchegov and Otto [J. Stat. Phys. 161(3), 553-576 (2015)] for a general mean-field setting that included the generalized Curie-Weiss-Potts model analyzed in the work of Jahnel et al. [Markov Process. Relat. Fields 20, 601-632 (2014)]. We use the aggregate path coupling method to identify and determine the threshold value βs separating the rapid and slow mixing regimes for the Glauber dynamics of the Potts model on Kn,n.

  5. Voter Model Perturbations and Reaction Diffusion Equations

    Cox, J Theodore; Perkins, Edwin


    We consider particle systems that are perturbations of the voter model and show that when space and time are rescaled the system converges to a solution of a reaction diffusion equation in dimensions $d \\ge 3$. Combining this result with properties of the PDE, some methods arising from a low density super-Brownian limit theorem, and a block construction, we give general, and often asymptotically sharp, conditions for the existence of non-trivial stationary distributions, and for extinction of one type. As applications, we describe the phase diagrams of three systems when the parameters are close to the voter model: (i) a stochastic spatial Lotka-Volterra model of Neuhauser and Pacala, (ii) a model of the evolution of cooperation of Ohtsuki, Hauert, Lieberman, and Nowak, and (iii) a continuous time version of the non-linear voter model of Molofsky, Durrett, Dushoff, Griffeath, and Levin. The first application confirms a conjecture of Cox and Perkins and the second confirms a conjecture of Ohtsuki et al in the ...

  6. A unified model of heading and path perception in primate MSTd.

    Oliver W Layton


    Full Text Available Self-motion, steering, and obstacle avoidance during navigation in the real world require humans to travel along curved paths. Many perceptual models have been proposed that focus on heading, which specifies the direction of travel along straight paths, but not on path curvature, which humans accurately perceive and is critical to everyday locomotion. In primates, including humans, dorsal medial superior temporal area (MSTd has been implicated in heading perception. However, the majority of MSTd neurons respond optimally to spiral patterns, rather than to the radial expansion patterns associated with heading. No existing theory of curved path perception explains the neural mechanisms by which humans accurately assess path and no functional role for spiral-tuned cells has yet been proposed. Here we present a computational model that demonstrates how the continuum of observed cells (radial to circular in MSTd can simultaneously code curvature and heading across the neural population. Curvature is encoded through the spirality of the most active cell, and heading is encoded through the visuotopic location of the center of the most active cell's receptive field. Model curvature and heading errors fit those made by humans. Our model challenges the view that the function of MSTd is heading estimation, based on our analysis we claim that it is primarily concerned with trajectory estimation and the simultaneous representation of both curvature and heading. In our model, temporal dynamics afford time-history in the neural representation of optic flow, which may modulate its structure. This has far-reaching implications for the interpretation of studies that assume that optic flow is, and should be, represented as an instantaneous vector field. Our results suggest that spiral motion patterns that emerge in spatio-temporal optic flow are essential for guiding self-motion along complex trajectories, and that cells in MSTd are specifically tuned to extract

  7. Culminating paths

    Mireille Bousquet-Mélou


    Full Text Available Let a and b be two positive integers. A culminating path is a path of ℤ 2 that starts from (0,0, consists of steps (1,a and (1,-b, stays above the x-axis and ends at the highest ordinate it ever reaches. These paths were first encountered in bioinformatics, in the analysis of similarity search algorithms. They are also related to certain models of Lorentzian gravity in theoretical physics. We first show that the language on a two letter alphabet that naturally encodes culminating paths is not context-free. Then, we focus on the enumeration of culminating paths. A step by step approach, combined with the kernel method, provides a closed form expression for the generating function of culminating paths ending at a (generic height k. In the case a = b, we derive from this expression the asymptotic behaviour of the number of culminating paths of length n. When a > b, we obtain the asymptotic behaviour by a simpler argument. When a < b, we only determine the exponential growth of the number of culminating paths. Finally, we study the uniform random generation of culminating paths via various methods. The rejection approach, coupled with a symmetry argument, gives an algorithm that is linear when a ≥ b, with no precomputation stage nor non-linear storage required. The choice of the best algorithm is not as clear when a < b. An elementary recursive approach yields a linear algorithm after a precomputation stage involving O (n 3 arithmetic operations, but we also present some alternatives that may be more efficient in practice.

  8. Modelling rapid subsurface flow at the hillslope scale with explicit representation of preferential flow paths

    Wienhöfer, J.; Zehe, E.


    Rapid lateral flow processes via preferential flow paths are widely accepted to play a key role for rainfall-runoff response in temperate humid headwater catchments. A quantitative description of these processes, however, is still a major challenge in hydrological research, not least because detailed information about the architecture of subsurface flow paths are often impossible to obtain at a natural site without disturbing the system. Our study combines physically based modelling and field observations with the objective to better understand how flow network configurations influence the hydrological response of hillslopes. The system under investigation is a forested hillslope with a small perennial spring at the study area Heumöser, a headwater catchment of the Dornbirnerach in Vorarlberg, Austria. In-situ points measurements of field-saturated hydraulic conductivity and dye staining experiments at the plot scale revealed that shrinkage cracks and biogenic macropores function as preferential flow paths in the fine-textured soils of the study area, and these preferential flow structures were active in fast subsurface transport of artificial tracers at the hillslope scale. For modelling of water and solute transport, we followed the approach of implementing preferential flow paths as spatially explicit structures of high hydraulic conductivity and low retention within the 2D process-based model CATFLOW. Many potential configurations of the flow path network were generated as realisations of a stochastic process informed by macropore characteristics derived from the plot scale observations. Together with different realisations of soil hydraulic parameters, this approach results in a Monte Carlo study. The model setups were used for short-term simulation of a sprinkling and tracer experiment, and the results were evaluated against measured discharges and tracer breakthrough curves. Although both criteria were taken for model evaluation, still several model setups

  9. A Geometry Model for Tortuosity of Flow Path in Porous Media

    YU Bo-Ming; LI Jian-Hua


    @@ A simple geometry model for tortuosity of flow path in porous media is proposed based on the assumption that some particles in a porous medium are unrestrictedly overlapped and the others are not. The proposed model is expressed as a function of porosity and there is no empirical constant in this model. The model predictions are compared with those from available correlations obtained numerically and experimentally, both of which are in agreement with each other. The present model can also give the tortuosity with a good approximation near the percolation threshold. The validity of the present tortuosity model is thus verified.

  10. Path loss modelling and comparison based on the radio propagation measurement at 3.5GHz

    Wang Ping; Li Yingzhe; Chang Ruoting; Sun Kun; Xu Hui


    Wideband IMT-Advanced mobile communication systems tend to operate in the high frequency bands due to a relatively large capacity available. Thus, Measurement and modelling methods of radio propagation characteristics are proposed for the field test of Chinese 4th generation (4G) trial system. The measurement system is established for 3.5GHz based on the sophisticated measurement instruments and the virtual instrument technology. The characteristic parameters of radio propagation such as path loss (PL) exponent and shadow fading standard deviation are extracted from measurement data, which result in the path loss model finally. The comparisons with other existing international models results validate our measurement in terms of path loss model. Based on the analysis of the existing extension model assumed for the microwave frequency at 3.5GHz, we find that the Stanford University Interim (SUI) model fits very well with the measurement result in the hotspot scenario, while the COST 231 model is closer to the measurement result in the suburban scenario. This result provides a measurement-based channel reference for the development of the future IMT-Advanced systems in China.

  11. Validation of Tilt Gain under Realistic Path Loss Model and Network Scenario

    Nguyen, Huan Cong; Rodriguez, Ignacio; Sørensen, Troels Bundgaard


    Despite being a simple and commonly-applied radio optimization technique, the impact on practical network performance from base station antenna downtilt is not well understood. Most published studies based on empirical path loss models report tilt angles and performance gains that are far higher...... than practical experience suggests. We motivate in this paper, based on a practical LTE scenario, that the discrepancy partly lies in the path loss model, and shows that a more detailed semi-deterministic model leads to both lower gains in terms of SINR, outage probability and downlink throughput...... settings, including the use of electrical and/or mechanical antenna downtilt, and therefore it is possible to find multiple optimum tilt profiles in a practical case. A broader implication of this study is that care must be taken when using the 3GPP model to evaluate advanced adaptive antenna techniques...

  12. Modeling of Reaction Processes Controlled by Diffusion

    Revelli, J


    Stochastic modeling is quite powerful in science and technology.The technics derived from this process have been used with great success in laser theory, biological systems and chemical reactions.Besides, they provide a theoretical framework for the analysis of experimental results on the field of particle's diffusion in ordered and disordered materials.In this work we analyze transport processes in one-dimensional fluctuating media, which are media that change their state in time.This fact induces changes in the movements of the particles giving rise to different phenomena and dynamics that will be described and analyzed in this work.We present some random walk models to describe these fluctuating media.These models include state transitions governed by different dynamical processes.We also analyze the trapping problem in a lattice by means of a simple model which predicts a resonance-like phenomenon.Also we study effective diffusion processes over surfaces due to random walks in the bulk.We consider differe...

  13. A Path Based Model for a Green Liner Shipping Network Design Problem

    Mads K. Jepsen; Berit Lofstedt; Christian E. M. Plum; David Pisinger; Mikkel M. Sigurd


    Liner shipping networks are the backbone of international trade providing low transportation cost, which is a major driver of globalization. These networks are under constant pressure to deliver capacity, cost effectiveness and environmentally conscious transport solutions. This article proposes a new path based MIP model for the Liner shipping Network Design Problem minimizing the cost of vessels and their fuel consumption facilitating a green network. The proposed model reduces problem size...

  14. Model Algorithm Research on Cooling Path Control of Hot-rolled Dual-phase Steel

    Xiao-qing XU; Xiao-dong HAO; Shi-guang ZHOU; Chang-sheng LIU; Qi-fu ZHANG


    With the development of advanced high strength steel,especially for dual-phase steel,the model algorithm for cooling control after hot rolling has to achieve the targeted coiling temperature control at the location of downcoiler whilst maintaining the cooling path control based on strip microstructure along the whole cooling section.A cooling path control algorithm was proposed for the laminar cooling process as a solution to practical difficulties associated with the realization of the thermal cycle during cooling process.The heat conduction equation coupled with the carbon diffusion equation with moving boundary was employed in order to simulate temperature change and phase transfor-mation kinetics,making it possible to observe the temperature field and the phase fraction of the strip in real time. On this basis,an optimization method was utilized for valve settings to ensure the minimum deviations between the predicted and actual cooling path of the strip,taking into account the constraints of the cooling equipment′s specific capacity,cooling line length,etc.Results showed that the model algorithm was able to achieve the online cooling path control for dual-phase steel.

  15. Study of Model Predictive Control for Path-Following Autonomous Ground Vehicle Control under Crosswind Effect

    Fitri Yakub


    Full Text Available We present a comparative study of model predictive control approaches of two-wheel steering, four-wheel steering, and a combination of two-wheel steering with direct yaw moment control manoeuvres for path-following control in autonomous car vehicle dynamics systems. Single-track mode, based on a linearized vehicle and tire model, is used. Based on a given trajectory, we drove the vehicle at low and high forward speeds and on low and high road friction surfaces for a double-lane change scenario in order to follow the desired trajectory as close as possible while rejecting the effects of wind gusts. We compared the controller based on both simple and complex bicycle models without and with the roll vehicle dynamics for different types of model predictive control manoeuvres. The simulation result showed that the model predictive control gave a better performance in terms of robustness for both forward speeds and road surface variation in autonomous path-following control. It also demonstrated that model predictive control is useful to maintain vehicle stability along the desired path and has an ability to eliminate the crosswind effect.

  16. Active control of structural vibration with on-line secondary path modeling

    YANG Tiejun; GU Zhongquan


    An active control strategy with on-line secondary path modeling is proposed and applied in active control of helicopter structural vibration. Computer simulations of the secondary path modeling performance demonstrate the superiorities of the active control strategy. A 2-input 4-output active control simulation for a helicopter model is performed and great reduction of structural vibration is achieved. 2-input 2-output and 2-input 4-output experimental studies of structural vibration control for a free-free beam are also carried out in laboratory to simulate a flying helicopter. The experimental results also show better reduction of the structural vibration, which verifies that the proposed method is effective and practical in structural vibration reduction.

  17. Understanding hydrological flow paths in conceptual catchment models using uncertainty and sensitivity analysis

    Mockler, Eva M.; O'Loughlin, Fiachra E.; Bruen, Michael


    Increasing pressures on water quality due to intensification of agriculture have raised demands for environmental modeling to accurately simulate the movement of diffuse (nonpoint) nutrients in catchments. As hydrological flows drive the movement and attenuation of nutrients, individual hydrological processes in models should be adequately represented for water quality simulations to be meaningful. In particular, the relative contribution of groundwater and surface runoff to rivers is of interest, as increasing nitrate concentrations are linked to higher groundwater discharges. These requirements for hydrological modeling of groundwater contribution to rivers initiated this assessment of internal flow path partitioning in conceptual hydrological models. In this study, a variance based sensitivity analysis method was used to investigate parameter sensitivities and flow partitioning of three conceptual hydrological models simulating 31 Irish catchments. We compared two established conceptual hydrological models (NAM and SMARG) and a new model (SMART), produced especially for water quality modeling. In addition to the criteria that assess streamflow simulations, a ratio of average groundwater contribution to total streamflow was calculated for all simulations over the 16 year study period. As observations time-series of groundwater contributions to streamflow are not available at catchment scale, the groundwater ratios were evaluated against average annual indices of base flow and deep groundwater flow for each catchment. The exploration of sensitivities of internal flow path partitioning was a specific focus to assist in evaluating model performances. Results highlight that model structure has a strong impact on simulated groundwater flow paths. Sensitivity to the internal pathways in the models are not reflected in the performance criteria results. This demonstrates that simulated groundwater contribution should be constrained by independent data to ensure results

  18. Model for reaction kinetics in pyrolysis of wood

    Ahuja, P.; Singh, P.C.; Upadhyay, S.N.; Kumar, S. [Banaras Hindu Univ., Varanasi (India)


    A reaction model for the pyrolysis of small and large particles of wood Is developed. The chemical reactions that take place when biomass is pyrolyzed are the devolatilization reactions (primary) and due to the vapour-solid interactions (secondary). In the case of small particles, when the volatiles are immediately removed by the purge gas, only primary reactions occur and the reaction model is described by weight loss and char forming reactions. The of heterogeneous secondary reactions occur in the case of large particles due to the interaction between the volatiles and the hot nascent primary char. A chain reaction mechanism of secondary char formation is proposed. The model takes both the volatiles retention time and cracking and repolymerization reactions of the vapours with the decomposing solid as well as autocatalysis into consideration. 7 refs., 3 figs., 2 tabs.

  19. Model for reaction kinetics in pyrolysis of wood

    Ahuja, P.; Singh, P.C.; Upadhyay, S.N.; Kuma, S. [Banaras Hindu Univ., Varanasi (India)


    A reaction model for the pyrolysis of small and large particles of wood is developed. The chemical reactions that take place when biomass is pyrolyzed are the devolatilization reactions (primary) and due to the vapour-solid interactions (secondary). In the case of small particles, when the volatiles are immediately removed by the purge gas, only primary reactions occur and the reaction model is described by weight loss and char forming reactions. The heterogeneous secondary reactions occur in the case of large particles due to the interaction between the volatiles and the hot nascent primary char. A chain reaction mechanism of secondary char formation is proposed. The model takes both the volatiles retention time and cracking and repolymerization reactions of the vapours with the decomposing solid as well as autocatalysis into consideration. 6 refs., 3 figs., 2 tabs.

  20. Crack path in liquid metal embrittlement: experiments with steels and modeling

    T. Auger


    Full Text Available We review the recent experimental clarification of the fracture path in Liquid Metal Embrittlement with austenitic and martensitic steels. Using state of the art characterization tools (Focused Ion Beam and Transmission Electron Microscopy a clear understanding of crack path is emerging for these systems where a classical fractographic analysis fails to provide useful information. The main finding is that most of the cracking process takes place at grain boundaries, lath or mechanical twin boundaries while cleavage or plastic flow localization is rarely the observed fracture mode. Based on these experimental insights, we sketch an on-going modeling strategy for LME crack initiation and propagation at mesoscopic scale. At the microstructural scale, crystal plasticity constitutive equations are used to model the plastic deformation in metals and alloys. The microstructure used is either extracted from experimental measurements by 3D-EBSD (Electron Back Scattering Diffraction or simulated starting from a Voronoï approach. The presence of a crackwithin the polycrystalline aggregate is taken into account in order to study the surrounding plastic dissipation and the crack path. One key piece of information that can be extracted is the typical order of magnitude of the stress-strain state at GB in order to constrain crack initiation models. The challenges of building predictive LME cracking models are outlined.

  1. All-pairs Shortest Path Algorithm based on MPI+CUDA Distributed Parallel Programming Model

    Qingshuang Wu


    Full Text Available In view of the problem that computing shortest paths in a graph is a complex and time-consuming process, and the traditional algorithm that rely on the CPU as computing unit solely can't meet the demand of real-time processing, in this paper, we present an all-pairs shortest paths algorithm using MPI+CUDA hybrid programming model, which can take use of the overwhelming computing power of the GPU cluster to speed up the processing. This proposed algorithm can combine the advantages of MPI and CUDA programming model, and can realize two-level parallel computing. In the cluster-level, we take use of the MPI programming model to achieve a coarse-grained parallel computing between the computational nodes of the GPU cluster. In the node-level, we take use of the CUDA programming model to achieve a GPU-accelerated fine grit parallel computing in each computational node internal. The experimental results show that the MPI+CUDA-based parallel algorithm can take full advantage of the powerful computing capability of the GPU cluster, and can achieve about hundreds of time speedup; The whole algorithm has good computing performance, reliability and scalability, and it is able to meet the demand of real-time processing of massive spatial shortest path analysis

  2. Littelmann path model for geometric crystals, Whittaker functions on Lie groups and Brownian motion

    Chhaibi, Reda


    Generally speaking, this thesis focuses on the interplay between the representations of Lie groups and probability theory. It subdivides into essentially three parts. In a first rather algebraic part, we construct a path model for geometric crystals in the sense of Berenstein and Kazhdan, for complex semi-simple Lie groups. We will mainly describe the algebraic structure, its natural morphisms and parameterizations. The theory of total positivity will play a particularly important role. Then, we anticipate on the probabilistic part by exhibiting a canonical measure on geometric crystals. It uses as ingredients the superpotential for the flag manifold and a measure invariant under the crystal actions. The image measure under the weight map plays the role of Duistermaat-Heckman measure. Its Laplace transform defines Whittaker functions, providing an interesting formula for all Lie groups. Then it appears clearly that Whittaker functions are to geometric crystals, what characters are to combinatorial crystals. The Littlewood-Richardson rule is also exposed. Finally we present the probabilistic approach that allows to find the canonical measure. It is based on the fundamental idea that the Wiener measure will induce the adequate measure on the algebraic structures through the path model. In the last chapter, we show how our geometric model degenerates to the continuous classical Littelmann path model and thus recover known results. For example, the canonical measure on a geometric crystal of highest weight degenerates into a uniform measure on a polytope, and recovers the parameterizations of continuous crystals.

  3. Modeling s-t Path Availability to Support Disaster Vulnerability Assessment of Network Infrastructure

    Matisziw, Timothy C


    The maintenance of system flow is critical for effective network operation. Any type of disruption to network facilities (arcs/nodes) potentially risks loss of service, leaving users without access to important resources. It is therefore an important goal of planners to assess infrastructures for vulnerabilities, identifying those vital nodes/arcs whose debilitation would compromise the most source-sink (s-t) interaction or system flow. Due to the budgetary limitations of disaster management agencies, protection/fortification and planning for the recovery of these vital infrastructure facilities is a logical and efficient proactive approach to reducing worst-case risk of service disruption. Given damage to a network, evaluating the potential for flow between s-t pairs requires assessing the availability of an operational s-t path. Recent models proposed for identifying infrastructure vital to system flow have relied on enumeration of all s-t paths to support this task. This paper proposes an alternative model...

  4. Modeling the average shortest-path length in growth of word-adjacency networks

    Kulig, Andrzej; DroŻdŻ, Stanisław; Kwapień, Jarosław; OświÈ©cimka, Paweł


    We investigate properties of evolving linguistic networks defined by the word-adjacency relation. Such networks belong to the category of networks with accelerated growth but their shortest-path length appears to reveal the network size dependence of different functional form than the ones known so far. We thus compare the networks created from literary texts with their artificial substitutes based on different variants of the Dorogovtsev-Mendes model and observe that none of them is able to properly simulate the novel asymptotics of the shortest-path length. Then, we identify the local chainlike linear growth induced by grammar and style as a missing element in this model and extend it by incorporating such effects. It is in this way that a satisfactory agreement with the empirical result is obtained.

  5. An Entropy-Based Approach to Path Analysis of Structural Generalized Linear Models: A Basic Idea

    Nobuoki Eshima


    Full Text Available A path analysis method for causal systems based on generalized linear models is proposed by using entropy. A practical example is introduced, and a brief explanation of the entropy coefficient of determination is given. Direct and indirect effects of explanatory variables are discussed as log odds ratios, i.e., relative information, and a method for summarizing the effects is proposed. The example dataset is re-analyzed by using the method.

  6. Evolutionistic or revolutionary paths? A PACS maturity model for strategic situational planning.

    van de Wetering, Rogier; Batenburg, Ronald; Lederman, Reeva


    While many hospitals are re-evaluating their current Picture Archiving and Communication System (PACS), few have a mature strategy for PACS deployment. Furthermore, strategies for implementation, strategic and situational planning methods for the evolution of PACS maturity are scarce in the scientific literature. Consequently, in this paper we propose a strategic planning method for PACS deployment. This method builds upon a PACS maturity model (PMM), based on the elaboration of the strategic alignment concept and the maturity growth path concept previously developed in the PACS domain. First, we review the literature on strategic planning for information systems and information technology and PACS maturity. Secondly, the PMM is extended by applying four different strategic perspectives of the Strategic Alignment Framework whereupon two types of growth paths (evolutionistic and revolutionary) are applied that focus on a roadmap for PMM. This roadmap builds a path to get from one level of maturity and evolve to the next. An extended method for PACS strategic planning is developed. This method defines eight distinctive strategies for PACS strategic situational planning that allow decision-makers in hospitals to decide which approach best suits their hospitals' current situation and future ambition and what in principle is needed to evolve through the different maturity levels. The proposed method allows hospitals to strategically plan for PACS maturation. It is situational in that the required investments and activities depend on the alignment between the hospital strategy and the selected growth path. The inclusion of both strategic alignment and maturity growth path concepts make the planning method rigorous, and provide a framework for further empirical research and clinical practice.

  7. Modeling of path delay in the neutral atmosphere: a paradigm shift

    Petrov, Leonid


    Computation of propagation effects in the neutral atmosphere, namely path delay, extinction, and bending angle is a trivial task provided the 4D state of the atmosphere is known. Unfortunately, the mixing ratio of water vapor is highly variable and it cannot be deduced from surface measurements. That fact led to a paradigm that considers path delay and extinction in the atmosphere as a~priori unknown quantities that have to be evaluated from the radio astronomy data themselves. Development of our ability to model the atmosphere and to digest humongous outputs of these models that took place over the course of the 21st century changed the game. Using the publicly available output of operational numerical weather model GEOS run by NASA, we are in a position to compute path delay through the neutral atmosphere for any station and for any epoch from 1979 through now with accuracy of 45 ps * cosec elevation. We are in a position to compute extinction with accuracy better than 10 pro cents. We are in a position to ...

  8. Multi-Dimensional Path Queries

    Bækgaard, Lars


    We present the path-relationship model that supports multi-dimensional data modeling and querying. A path-relationship database is composed of sets of paths and sets of relationships. A path is a sequence of related elements (atoms, paths, and sets of paths). A relationship is a binary path...... to create nested path structures. We present an SQL-like query language that is based on path expressions and we show how to use it to express multi-dimensional path queries that are suited for advanced data analysis in decision support environments like data warehousing environments...

  9. Path integral representation of spin foam models of 4d gravity

    Conrady, Florian


    We give a unified description of all recent spin foam models introduced by Engle, Livine, Pereira and Rovelli (ELPR) and by Freidel and Krasnov (FK). We show that the FK models are, for all values of the Immirzi parameter, equivalent to path integrals of a discrete theory and we provide an explicit formula for the associated actions. We discuss the relation between the FK and ELPR models and also study the corresponding boundary states. For general Immirzi parameter, these are given by Alexandrov's and Livine's SO(4) projected states. For 0 <= gamma < 1, the states can be restricted to SU(2) spin networks.

  10. Path dependent models to predict property changes in graphite irradiated at changing irradiation temperatures

    Kok, S


    Full Text Available property curves are removed by an exponentially decaying function. The method is illustrated in Figure 1. Figure 1: Illustration of scaled fluence method STATE VARIABLE EVOLUTION MODEL In this work, path dependency is accounted for by using a state... variable evolution model. A property P is evolved by integrating an evolution equation of the form . Here ? is the fluence, f is the evolution equation and T is the irradiation temperature. Such an internal state variable model is similar to the metal...

  11. Modeling of hydrogen evolution reaction on the surface of GaInP2

    Choi, Woon Ih; Wood, Brandon; Schwegler, Eric; Ogitsu, Tadashi


    GaInP2 is promising candidate material for hydrogen production using sunlight. It reduces solvated proton into hydrogen molecule using light-induced excited electrons in the photoelectrochemical cell. However, it is challenging to model hydrogen evolution reaction (HER) using first-principles molecular dynamics. Instead, we use Anderson-Newns model and generalized solvent coordinate in Marcus-Hush theory to describe adiabatic free energy surface of HER. Model parameters are fitted from the DFT calculations. We model Volmer-Heyrovsky reaction path on the surfaces of CuPt phase of GaInP2. We also discuss effects of surface oxide and catalyst atoms that exist on top of bare surfaces in experimental circumstances.

  12. Novel Congestion-Free Alternate Routing Path Scheme using Stackelberg Game Theory Model in Wireless Networks

    P. Chitra


    Full Text Available Recently, wireless network technologies were designed for most of the applications. Congestion raised in the wireless network degrades the performance and reduces the throughput. Congestion-free network is quit essen- tial in the transport layer to prevent performance degradation in a wireless network. Game theory is a branch of applied mathematics and applied sciences that used in wireless network, political science, biology, computer science, philosophy and economics. e great challenges of wireless network are their congestion by various factors. E ective congestion-free alternate path routing is pretty essential to increase network performance. Stackelberg game theory model is currently employed as an e ective tool to design and formulate conges- tion issues in wireless networks. is work uses a Stackelberg game to design alternate path model to avoid congestion. In this game, leaders and followers are selected to select an alternate routing path. e correlated equilibrium is used in Stackelberg game for making better decision between non-cooperation and cooperation. Congestion was continuously monitored to increase the throughput in the network. Simulation results show that the proposed scheme could extensively improve the network performance by reducing congestion with the help of Stackelberg game and thereby enhance throughput.

  13. Neural Network Model for Path-Planning of Robotic Rover Systems

    Bassil, Youssef


    Today, robotics is an auspicious and fast-growing branch of technology that involves the manufacturing, design, and maintenance of robot machines that can operate in an autonomous fashion and can be used in a wide variety of applications including space exploration, weaponry, household, and transportation. More particularly, in space applications, a common type of robots has been of widespread use in the recent years. It is called planetary rover which is a robot vehicle that moves across the surface of a planet and conducts detailed geological studies pertaining to the properties of the landing cosmic environment. However, rovers are always impeded by obstacles along the traveling path which can destabilize the rover's body and prevent it from reaching its goal destination. This paper proposes an ANN model that allows rover systems to carry out autonomous path-planning to successfully navigate through challenging planetary terrains and follow their goal location while avoiding dangerous obstacles. The propos...

  14. Calculation of the Model of Coesite Inclusions and Analysis of Their Retrometamorphic Paths

    MENG Dawei; DING Xiaokun; WU Xiuling


    The process and path of retrometamorphism of coesite have great significance to our understanding of the PT tracks of the exhumation of ultrahigh-pressure metamorphic rocks. Most of the coesites in the eclogite from Shima,Anhui Province, the Dabie Mountains, China, are found degraded to quartz partly or wholly, with ruptures occurring in the shells, outside which include the coesite and quartz According to the microscopic observation, the sample of coesite inclusion is composed of garnet, quartz and coesite, based on which we have built a three-shelled composite sphere model to compute the transition of coesite. Based on the crystal growth formulas and pressure conditions of the ruptures in the garnet, we have calculated the radius of the quartz sphere, which depends on temperature, and eventually drawn the different retrometamorphic paths for different retrometamorphism rates.

  15. Constrained-path quantum Monte Carlo approach for non-yrast states within the shell model

    Bonnard, J. [INFN, Sezione di Padova, Padova (Italy); LPC Caen, ENSICAEN, Universite de Caen, CNRS/IN2P3, Caen (France); Juillet, O. [LPC Caen, ENSICAEN, Universite de Caen, CNRS/IN2P3, Caen (France)


    The present paper intends to present an extension of the constrained-path quantum Monte Carlo approach allowing to reconstruct non-yrast states in order to reach the complete spectroscopy of nuclei within the interacting shell model. As in the yrast case studied in a previous work, the formalism involves a variational symmetry-restored wave function assuming two central roles. First, it guides the underlying Brownian motion to improve the efficiency of the sampling. Second, it constrains the stochastic paths according to the phaseless approximation to control sign or phase problems that usually plague fermionic QMC simulations. Proof-of-principle results in the sd valence space are reported. They prove the ability of the scheme to offer remarkably accurate binding energies for both even- and odd-mass nuclei irrespective of the considered interaction. (orig.)

  16. Projects Delay Factors of Saudi Arabia Construction Industry Using PLS-SEM Path Modelling Approach

    Abdul RahmanIsmail


    Full Text Available This paper presents the development of PLS-SEM Path Model of delay factors of Saudi Arabia construction industry focussing on Mecca City. The model was developed and assessed using SmartPLS v3.0 software and it consists of 37 factors/manifests in 7 groups/independent variables and one dependent variable which is delay of the construction projects. The model was rigorously assessed at measurement and structural components and the outcomes found that the model has achieved the required threshold values. At structural level of the model, among the seven groups, the client and consultant group has the highest impact on construction delay with path coefficient β-value of 0.452 and the project management and contract administration group is having the least impact to the construction delay with β-value of 0.016. The overall model has moderate explaining power ability with R2 value of 0.197 for Saudi Arabia construction industry representation. This model will able to assist practitioners in Mecca city to pay more attention in risk analysis for potential construction delay.

  17. Pedestrian flow-path modeling to support tsunami-evacuation planning

    Wood, N. J.; Jones, J. M.; Schmidtlein, M.


    Near-field tsunami hazards are credible threats to many coastal communities throughout the world. Along the U.S. Pacific Northwest coast, low-lying areas could be inundated by a series of catastrophic tsunamis potentially arriving in a matter of minutes following a Cascadia subduction zone (CSZ) earthquake. We developed a geospatial-modeling method for characterizing pedestrian-evacuation flow paths and evacuation basins to support evacuation and relief planning efforts for coastal communities in this region. We demonstrate this approach using the coastal communities of Aberdeen, Hoquiam, and Cosmopolis in southwestern Grays Harbor County, Washington (USA), where previous research suggests approximately 20,500 people (99% of the residents in tsunami-hazard zones) will likely have enough time to evacuate before tsunami-wave arrival. Geospatial, anisotropic, path distance models were developed to map the most efficient pedestrian paths to higher ground from locations within the tsunami-hazard zone. This information was then used to identify evacuation basins, outlining neighborhoods sharing a common evacuation pathway to safety. We then estimated the number of people traveling along designated evacuation pathways and arriving at pre-determined safe assembly areas, helping determine shelter demand and relief support (e.g., for elderly individuals or tourists). Finally, we assessed which paths may become inaccessible due to earthquake-induced ground failures, a factor which may impact an individual's success in reaching safe ground. The presentation will include a discussion of the implications of our analysis for developing more comprehensive coastal community tsunami-evacuation planning strategies worldwide.

  18. A computational study of pyrolysis reactions of lignin model compounds

    Thomas Elder


    Enthalpies of reaction for the initial steps in the pyrolysis of lignin have been evaluated at the CBS-4m level of theory using fully substituted b-O-4 dilignols. Values for competing unimolecular decomposition reactions are consistent with results previously published for phenethyl phenyl ether models, but with lowered selectivity. Chain propagating reactions of free...

  19. Polymerization as a Model Chain Reaction

    Morton, Maurice


    Describes the features of the free radical, anionic, and cationic mechanisms of chain addition polymerization. Indicates that the nature of chain reactions can be best taught through the study of macromolecules. (CC)

  20. Reaction Wheel Disturbance Model Extraction Software Project

    National Aeronautics and Space Administration — Reaction wheel mechanical noise is one of the largest sources of disturbance forcing on space-based observatories. Such noise arises from mass imbalance, bearing...

  1. Reaction Wheel Disturbance Model Extraction Software Project

    National Aeronautics and Space Administration — Reaction wheel disturbances are some of the largest sources of noise on sensitive telescopes. Such wheel-induced mechanical noises are not well characterized....

  2. A path based model for a green liner shipping network design problem

    Jepsen, Mads Kehlet; Brouer, Berit Dangaard; Plum, Christian Edinger Munk


    Liner shipping networks are the backbone of international trade providing low transportation cost, which is a major driver of globalization. These networks are under constant pressure to deliver capacity, cost effectiveness and environmentally conscious transport solutions. This article proposes...... a new path based MIP model for the Liner shipping Network Design Problem minimizing the cost of vessels and their fuel consumption facilitating a green network. The proposed model reduces problem size using a novel aggregation of demands. A decomposition method enabling delayed column generation...

  3. Micromechanical modelling of the elastoplastic behaviour of metallic material under strain-path changes

    Fajoui, Jamal; Gloaguen, David; Courant, Bruno; Guillén, Ronald


    A two-level homogenization approach is applied for the micromechanical modelling of the elastoplastic material behaviour during various strain-path changes. A mechanical description of the grain is developed through a micro-meso transition based on a modified elastoplastic self-consistent approach which takes into account the dislocation evolution. Next, a meso-macro transition using a self-consistent model is used to deduce the macroscopic behaviour of the polycrystal. A correct agreement is observed between the simulations and the experimental results at the mesoscopic and macroscopic levels.

  4. Light Path Model of Fiber Optic Liquid Level Sensor Considering Residual Liquid Film on the Wall

    Zhijun Zhang


    Full Text Available The working principle of the refractive-type fiber optic liquid level sensor is analyzed in detail based on the light refraction principle. The optic path models are developed in consideration of common simplification and the residual liquid film on the glass tube wall. The calculating formulae for the model are derived, constraint conditions are obtained, influencing factors are discussed, and the scopes and skills of application are analyzed through instance simulations. The research results are useful in directing the correct usage of the fiber optic liquid level sensor, especially in special cases, such as those involving viscous liquid in the glass tube monitoring.

  5. Modelling Chemical Reasoning to Predict and Invent Reactions.

    Segler, Marwin H S; Waller, Mark P


    The ability to reason beyond established knowledge allows organic chemists to solve synthetic problems and invent novel transformations. Herein, we propose a model that mimics chemical reasoning, and formalises reaction prediction as finding missing links in a knowledge graph. We have constructed a knowledge graph containing 14.4 million molecules and 8.2 million binary reactions, which represents the bulk of all chemical reactions ever published in the scientific literature. Our model outperforms a rule-based expert system in the reaction prediction task for 180 000 randomly selected binary reactions. The data-driven model generalises even beyond known reaction types, and is thus capable of effectively (re-)discovering novel transformations (even including transition metal-catalysed reactions). Our model enables computers to infer hypotheses about reactivity and reactions by only considering the intrinsic local structure of the graph and because each single reaction prediction is typically achieved in a sub-second time frame, the model can be used as a high-throughput generator of reaction hypotheses for reaction discovery.

  6. Importance of cytochromes in cyclization reactions: quantum chemical study on a model reaction of proguanil to cycloguanil.

    Arfeen, Minhajul; Patel, Dhilon S; Abbat, Sheenu; Taxak, Nikhil; Bharatam, Prasad V


    Proguanil, an anti-malarial prodrug, undergoes cytochrome P450 catalyzed biotransformation to the pharmacologically active triazine metabolite (cycloguanil), which inhibits plasmodial dihydrofolate reductase. This cyclization is catalyzed by CYP2C19 and many anti-malarial lead compounds are being designed and synthesized to exploit this pathway. Quantum chemical calculations were performed using the model species (Cpd I for active species of cytochrome and N4-isopropyl-N6-methylbiguanide for proguanil) to elucidate the mechanism of the cyclization pathway. The overall reaction involves the loss of a water molecule, and is exothermic by approximately 55 kcal/mol, and involves a barrier of approximately 17 kcal/mol. The plausible reaction pathway involves the initial H-radical abstraction from the isopropyl group by Cpd I, followed by two alternative paths- (i) oxygen rebound to provide hydroxyl derivative and (ii) loss of additional H-radical to yield 1,3,5-triazatriene, which undergoes cyclization. This study helped in understanding the role of the active species of cytochromes in this important cyclization reaction. Copyright © 2014 Wiley Periodicals, Inc.

  7. Detailed reduction of reaction mechanisms for flame modeling

    Wang, Hai; Frenklach, Michael


    A method for reduction of detailed chemical reaction mechanisms, introduced earlier for ignition system, was extended to laminar premixed flames. The reduction is based on testing the reaction and reaction-enthalpy rates of the 'full' reaction mechanism using a zero-dimensional model with the flame temperature profile as a constraint. The technique is demonstrated with numerical tests performed on the mechanism of methane combustion.

  8. Including lateral interactions into microkinetic models of catalytic reactions

    Hellman, Anders; Honkala, Johanna Karoliina


    In many catalytic reactions lateral interactions between adsorbates are believed to have a strong influence on the reaction rates. We apply a microkinetic model to explore the effect of lateral interactions and how to efficiently take them into account in a simple catalytic reaction. Three differ...... different approximations are investigated: site, mean-field, and quasichemical approximations. The obtained results are compared to accurate Monte Carlo numbers. In the end, we apply the approximations to a real catalytic reaction, namely, ammonia synthesis....

  9. Nonadiabatic transition path sampling

    Sherman, M. C.; Corcelli, S. A.


    Fewest-switches surface hopping (FSSH) is combined with transition path sampling (TPS) to produce a new method called nonadiabatic path sampling (NAPS). The NAPS method is validated on a model electron transfer system coupled to a Langevin bath. Numerically exact rate constants are computed using the reactive flux (RF) method over a broad range of solvent frictions that span from the energy diffusion (low friction) regime to the spatial diffusion (high friction) regime. The NAPS method is shown to quantitatively reproduce the RF benchmark rate constants over the full range of solvent friction. Integrating FSSH within the TPS framework expands the applicability of both approaches and creates a new method that will be helpful in determining detailed mechanisms for nonadiabatic reactions in the condensed-phase.

  10. Adjoint LMS (ALMS Algorithm Based Active Noise Control with Feedback Path Modeling

    U Ramachandraiah,


    Full Text Available In active noise control (ANC systems, there exists an inherent feedback from the loudspeaker to the primary microphone. Adjoint least mean square (ALMS algorithm is known to be an alternative to the widely used filtered x LMS (FxLMS for reducing the computational complexity and memory requirements, especially in the case of multi-channel systems. Further FxLMS algorithm is based on the assumptionthat the order of the weighing filter and secondary path can be commuted which is not always true in practice. Though ALMS do not make such an assumption, neither FxLMS nor the ALMS algorithms onsider the feedback path effect that is inherent in ANC systems.We propose a feedback ANC system based on ALMS algorithm which is analogous to the system based on FxLMS. Detailed computational complexity analysis for addition and multiplication requirements ispresented and are compared with those of its counterpart to establish its usefulness. Simulation results show the convergence characteristics of the ALMS based ANC with feedback path modeling is on par with that based on FxLMS.

  11. A Minimal Path Searching Approach for Active Shape Model (ASM)-based Segmentation of the Lung.

    Guo, Shengwen; Fei, Baowei


    We are developing a minimal path searching method for active shape model (ASM)-based segmentation for detection of lung boundaries on digital radiographs. With the conventional ASM method, the position and shape parameters of the model points are iteratively refined and the target points are updated by the least Mahalanobis distance criterion. We propose an improved searching strategy that extends the searching points in a fan-shape region instead of along the normal direction. A minimal path (MP) deformable model is applied to drive the searching procedure. A statistical shape prior model is incorporated into the segmentation. In order to keep the smoothness of the shape, a smooth constraint is employed to the deformable model. To quantitatively assess the ASM-MP segmentation, we compare the automatic segmentation with manual segmentation for 72 lung digitized radiographs. The distance error between the ASM-MP and manual segmentation is 1.75 ± 0.33 pixels, while the error is 1.99 ± 0.45 pixels for the ASM. Our results demonstrate that our ASM-MP method can accurately segment the lung on digital radiographs.

  12. A minimal path searching approach for active shape model (ASM)-based segmentation of the lung

    Guo, Shengwen; Fei, Baowei


    We are developing a minimal path searching method for active shape model (ASM)-based segmentation for detection of lung boundaries on digital radiographs. With the conventional ASM method, the position and shape parameters of the model points are iteratively refined and the target points are updated by the least Mahalanobis distance criterion. We propose an improved searching strategy that extends the searching points in a fan-shape region instead of along the normal direction. A minimal path (MP) deformable model is applied to drive the searching procedure. A statistical shape prior model is incorporated into the segmentation. In order to keep the smoothness of the shape, a smooth constraint is employed to the deformable model. To quantitatively assess the ASM-MP segmentation, we compare the automatic segmentation with manual segmentation for 72 lung digitized radiographs. The distance error between the ASM-MP and manual segmentation is 1.75 +/- 0.33 pixels, while the error is 1.99 +/- 0.45 pixels for the ASM. Our results demonstrate that our ASM-MP method can accurately segment the lung on digital radiographs.

  13. Channeling the SmI₂ reactions to the radical path: radicals resisting reduction by SmI₂.

    Yella, Ramesh; Hoz, Shmaryahu


    Studies on the reaction of 4-(2,2-diphenylvinyl)pyridine with SmI2 revealed that the intermediate radical strongly resists further reduction to the corresponding anion. The resistance of the radical to accepting another electron is traced to its stabilization by the nitrogen lone pair. The literature suggests that oxygen may also play a role similar to that of nitrogen in directing the course of the reaction toward radical rather than to anionic chemistry.

  14. Vibroacoustic Modeling and Path Control of Air-Borne Axle Whine Noise

    Dong Guo


    Full Text Available The axle whine noise will eventually affect the vehicle noise performance. In this study, a systematic modeling approach is developed to analyze the axle whine problem by considering the hypoid gear mesh from the tooth contact process as well as the system dynamics effect with gear design parameters and shaft-bearing-housing system taken into account. Moreover, the tuning of the dominant air-borne path is modeled analytically by using the sound transmission loss idea. First, gear tooth load distribution results are obtained in a 3-dimensional loaded tooth contact analysis program. Then mesh parameters are synthesized and applied to a linear multibody gear dynamic model to obtain dynamic mesh and bearing responses. The bearing responses are used as the excitation force to a housing finite element model. Finally, the vibroacoustic analysis of the axle is performed using the boundary element method; sound pressure responses in the axle surface are then simulated. Transmission losses of different panel partitions are included in the final stage to guide the tuning of air-borne paths to reduce the radiated axle whine noise. The proposed approach gives a more in-depth understanding of the axle whine generation and therefore can further facilitate the system design and trouble-shooting.

  15. Family support and acceptance, gay male identity formation, and psychological adjustment: a path model.

    Elizur, Y; Ziv, M


    While heterosexist family undermining has been demonstrated to be a developmental risk factor in the life of persons with same-gender orientation, the issue of protective family factors is both controversial and relatively neglected. In this study of Israeli gay males (N = 114), we focused on the interrelations of family support, family acceptance and family knowledge of gay orientation, and gay male identity formation, and their effects on mental health and self-esteem. A path model was proposed based on the hypotheses that family support, family acceptance, family knowledge, and gay identity formation have an impact on psychological adjustment, and that family support has an effect on gay identity formation that is mediated by family acceptance. The assessment of gay identity formation was based on an established stage model that was streamlined for cross-cultural practice by defining three basic processes of same-gender identity formation: self-definition, self-acceptance, and disclosure (Elizur & Mintzer, 2001). The testing of our conceptual path model demonstrated an excellent fit with the data. An alternative model that hypothesized effects of gay male identity on family acceptance and family knowledge did not fit the data. Interpreting these results, we propose that the main effect of family support/acceptance on gay identity is related to the process of disclosure, and that both general family support and family acceptance of same-gender orientation play a significant role in the psychological adjustment of gay men.

  16. Exploring Hydrological Flow Paths in Conceptual Catchment Models using Variance-based Sensitivity Analysis

    Mockler, E. M.; O'Loughlin, F.; Bruen, M. P.


    Conceptual rainfall runoff (CRR) models aim to capture the dominant hydrological processes in a catchment in order to predict the flows in a river. Most flood forecasting models focus on predicting total outflows from a catchment and often perform well without the correct distribution between individual pathways. However, modelling of water flow paths within a catchment, rather than its overall response, is specifically needed to investigate the physical and chemical transport of matter through the various elements of the hydrological cycle. Focus is increasingly turning to accurately quantifying the internal movement of water within these models to investigate if the simulated processes contributing to the total flows are realistic in the expectation of generating more robust models. Parameter regionalisation is required if such models are to be widely used, particularly in ungauged catchments. However, most regionalisation studies to date have typically consisted of calibrations and correlations of parameters with catchment characteristics, or some variations of this. In order for a priori parameter estimation in this manner to be possible, a model must be parametrically parsimonious while still capturing the dominant processes of the catchment. The presence of parameter interactions within most CRR model structures can make parameter prediction in ungauged basins very difficult, as the functional role of the parameter within the model may not be uniquely identifiable. We use a variance based sensitivity analysis method to investigate parameter sensitivities and interactions in the global parameter space of three CRR models, simulating a set of 30 Irish catchments within a variety of hydrological settings over a 16 year period. The exploration of sensitivities of internal flow path partitioning was a specific focus and correlations between catchment characteristics and parameter sensitivities were also investigated to assist in evaluating model performances

  17. Testing an Integrated Self-Determined Work Motivation Model for People With Disabilities: A Path Analysis.

    Tansey, Timothy N; Iwanaga, Kanako; Bezyak, Jill; Ditchman, Nicole


    Individuals with disabilities are more likely to live in poverty, have more health issues, and be less likely to be employed than their same-aged peers. Although these issues may be attenuated by vocational rehabilitation services, amotivation and ambivalence to employment can limit the readiness of persons with disabilities to engage in these services. Drawing on self-efficacy, self-determination, and stages of change theories, the purpose of this study was to develop and test an integrated self-determined work motivation model for people with disabilities. Participants included 277 people with disabilities recruited through vocational rehabilitation agencies across 8 states. Path analysis was used to evaluate the contribution of functional disability, self-determination, and social efficacy variables in a hypothesized integrated self-determined work motivation model. Model estimations used maximum likelihood estimation and model-data fit was examined using several goodness-of-fit indices. The initial path analysis indicated a less than optimal fit between the model and the observed data. Post hoc model modifications were conducted based on examination of the critical ratios and modification indices and theoretical consideration. The respecified integrated self-determined work motivation model fit the data very well, χ2/df = 1.88, CFI = .99, and RMSEA = 0.056. The R2 for the endogenous variables in the model ranged from .19 to .54. Findings from this study support the integrated self-determined work motivation model in vocational rehabilitation as a useful framework for understanding the relationship among functioning levels, self-determination and self-efficacy factors, vocational rehabilitation engagement, and readiness for employment. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

  18. Unusual reaction paths of S{sub N}2 nucleophile substitution reactions CH{sub 4} + H{sup −} → CH{sub 4} + H{sup −} and CH{sub 4} + F{sup −} → CH{sub 3}F + H{sup −}: Quantum chemical calculations

    Minyaev, Ruslan M., E-mail: [Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka Ave., Rostov-on-Don 344090 (Russian Federation); Quapp, Wolfgang; Schmidt, Benjamin [Leipzig University, Mathematical Institute, Augustusplatz, D-04109 Leipzig (Germany); Getmanskii, Ilya V.; Koval, Vitaliy V. [Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka Ave., Rostov-on-Don 344090 (Russian Federation)


    Highlights: • High level quantum chemical calculations are performed for two S{sub N}2 reactions. • The calculated gradient reaction pathways for reactions have an unusual behavior. • An unusual saddle point of index two lies on the gradient reaction path. • VRI points have been detected by using Newton trajectories for the reaction path. • An infinite flow of gradient lines emanates at three equivalent product minima. - Abstract: 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 S{sub N}2 nucleophile substitution reactions CH{sub 4} + H{sup −} → CH{sub 4} + H{sup −} and CH{sub 4} + F{sup −} → CH{sub 3}F + H{sup −}. 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.

  19. Modeling the isotope effect in Walden inversion reactions

    Schechter, Israel


    A simple model to explain the isotope effect in the Walden exchange reaction is suggested. It is developed in the spirit of the line-of-centers models, and considers a hard-sphere collision that transfers energy from the relative translation to the desired vibrational mode, as well as geometrical properties and steric requirements. This model reproduces the recently measured cross sections for the reactions of hydrogen with isotopic silanes and older measurements of the substitution reactions of tritium atoms with isotopic methanes. Unlike previously given explanations, this model explains the effect of the attacking atom as well as of the other participating atoms. The model provides also qualitative explanation of the measured relative yields and thresholds of CH 3T and CH 2TF from the reaction T + CH 3F. Predictions for isotope effects and cross sections of some unmeasured reactions are given.

  20. Path planning versus cue responding: a bio-inspired model of switching between navigation strategies.

    Dollé, Laurent; Sheynikhovich, Denis; Girard, Benoît; Chavarriaga, Ricardo; Guillot, Agnès


    In this article, we describe a new computational model of switching between path-planning and cue-guided navigation strategies. It is based on three main assumptions: (i) the strategies are mediated by separate memory systems that learn independently and in parallel; (ii) the learning algorithms are different in the two memory systems-the cue-guided strategy uses a temporal-difference (TD) learning rule to approach a visible goal, whereas the path-planning strategy relies on a place-cell-based graph-search algorithm to learn the location of a hidden goal; (iii) a strategy selection mechanism uses TD-learning rule to choose the most successful strategy based on past experience. We propose a novel criterion for strategy selection based on the directions of goal-oriented movements suggested by the different strategies. We show that the selection criterion based on this "common currency" is capable of choosing the best among TD-learning and planning strategies and can be used to solve navigational tasks in continuous state and action spaces. The model has been successfully applied to reproduce rat behavior in two water-maze tasks in which the two strategies were shown to interact. The model was used to analyze competitive and cooperative interactions between different strategies during these tasks as well as relative influence of different types of sensory cues.

  1. Neutron Transfer Reactions on Neutron-Rich N=50 and N=82 Nuclei Near the r-Process Path

    Cizewski, J. A. [Rutgers University; Jones, K. L. [University of Tennessee, Knoxville (UTK); Kozub, R. L. [Tennessee Technological University; Pain, S. D. [Rutgers University; Thomas, J. S. [Rutgers University; Arbanas, Goran [ORNL; Adekola, Aderemi S [ORNL; Bardayan, Daniel W [ORNL; Blackmon, Jeff C [ORNL; Chae, K. Y. [University of Tennessee, Knoxville (UTK); Chipps, K. [Colorado School of Mines, Golden; Dean, David Jarvis [ORNL; Erikson, Luke [Colorado School of Mines, Golden; Gaddis, A. L. [Furman University; Harlin, Christopher W [ORNL; Hatarik, Robert [Rutgers University; Howard, Joshua A [ORNL; Johnson, Micah [ORNL; Kapler, R. [University of Tennessee, Knoxville (UTK); Krolas, W. [University of Warsaw; Liang, J Felix [ORNL; Livesay, Jake [ORNL; Ma, Zhanwen [ORNL; Matei, Catalin [Oak Ridge Associated Universities (ORAU); Moazen, Brian [University of Tennessee, Knoxville (UTK); Nesaraja, Caroline D [ORNL; O' Malley, Patrick [Rutgers University; Paulauskas, Stanley V [ORNL; Shapira, Dan [ORNL; ShrinerJr., J. F. [Tennessee Technological University; Sissom, D. J. [Tennessee Technological University; Smith, Michael Scott [ORNL; Swan, T. P. [University of Surrey, UK; Wilson, Gemma L [ORNL


    Neutron transfer (d,p) reaction studies on the N = 50 isotones, 82Ge and 84Se, and A{approx}130 nuclei, 130,132Sn and 134Te, have been measured. Direct neutron capture cross sections for 82Ge and 84Se (n,?) have been calculated and are combined with Hauser-Feshbach expectations to estimate total (n,?) cross sections. The A{approx}130 studies used an early implementation of the ORRUBA array of position-sensitive silicon strip detectors for reaction proton measurements. Preliminary excitation energy and angular distribution results from the A{approx}130 measurements are reported.

  2. Path analysis of the chronicity of depression using the comprehensive developmental model framework.

    Fandiño-Losada, Andrés; Bangdiwala, Shrikant I; Lavebratt, Catharina; Forsell, Yvonne


    Background Depressive disorder is recognized as recurrent or chronic in the majority of affected individuals; but literature is not consistent about determinants of the disorder course. Aims To analyse the relationships between familial, personal and environmental characteristics in different life phases and their effects on the chronicity of depression in a population-based sample. Methods It was a longitudinal panel study with three waves (W1-W3) for 651 adult men and women with diagnosis of minor/major depression or dysthymia at W1 of the Swedish PART (mental health, work and relations) study. Risk factors and co-morbidities were assessed with questionnaires. The main outcome was an episode of minor/major depression or dysthymia at 10-12 years of follow-up (W3). Liability for depressive episodes was determined using exploratory structural equation modelling (SEM), following a path approach with step-wise specification searches. Results Most of the risk factors determined, directly or indirectly, depression severity at W3. Somatic trait anxiety, partner loss and other negative life events at W1, depressive symptoms at W2, and life difficulties and other dependent life events at W3 had direct effects on the outcome. Conclusions SEM model revealed complex and intertwined psychopathological pathways leading to chronicity of depression, given previous episodes, which could be assembled in two main mechanisms: a depressive-internalizing path and an adversity path comprised of life events. Pathways are simpler than those of depression occurrence, emphasizing the relevance of personality factors as depression determinants, and excluding disability levels, co-morbidities and social support. These novel findings need to be replicated in future studies.

  3. DSMC Modeling of Flows with Recombination Reactions


    rarefied gas dynamics community has seen the development of efficient algorithms for modern computer architectures16–19 which dramatically expand the area of...that participate in recombination. ACKNOWLEDGMENTS The work was supported by the Air Force Office of Sci - entific Research (Program Officer Dr. Ivett...flow,” Prog. Aerosp. Sci . 72, 66–79 (2015). 14R. D. Levine,Molecular Reaction Dynamics (Cambridge University Press, Cambridge, 2005). 15A. Alexeenko and

  4. Limits to the critical current in Bi2Sr2Ca2Cu3Ox tape conductors: The parallel path model

    van der Laan, D.C.; Schwartz, J.; ten Haken, Bernard; Dhalle, M.; van Eck, H.J.N.


    An extensive overview of a model that describes current flow and dissipation in high-quality Bi2Sr2Ca2Cu3Ox superconducting tapes is provided. The parallel path model is based on a superconducting current running in two distinct parallel paths. One of the current paths is formed by grains that are

  5. Effect of reactions in small eddies on biomass gasification with eddy dissipation concept - Sub-grid scale reaction model.

    Chen, Juhui; Yin, Weijie; Wang, Shuai; Meng, Cheng; Li, Jiuru; Qin, Bai; Yu, Guangbin


    Large-eddy simulation (LES) approach is used for gas turbulence, and eddy dissipation concept (EDC)-sub-grid scale (SGS) reaction model is employed for reactions in small eddies. The simulated gas molar fractions are in better agreement with experimental data with EDC-SGS reaction model. The effect of reactions in small eddies on biomass gasification is emphatically analyzed with EDC-SGS reaction model. The distributions of the SGS reaction rates which represent the reactions in small eddies with particles concentration and temperature are analyzed. The distributions of SGS reaction rates have the similar trend with those of total reactions rates and the values account for about 15% of the total reactions rates. The heterogeneous reaction rates with EDC-SGS reaction model are also improved during the biomass gasification process in bubbling fluidized bed.

  6. Enzymatic circularization of a malto-octaose linear chain studied by stochastic reaction path calculations on cyclodextrin glycosyltransferase

    Uitdehaag, Joost C.M.; Veen, Bart A. van der; Dijkhuizen, Lubbert; Elber, Ron; Dijkstra, Bauke W.


    Cyclodextrin glycosyltransferase (CGTase) is an enzyme belonging to the ol-amylase family that forms cyclodextrins (circularly linked oligosaccharides) from starch. X-ray work has indicated that this cyclization reaction of CGTase involves a 23-Angstrom movement of the nonreducing end of a linear ma

  7. Affordances perspective and grammaticalization: Incorporation of language, environment and users in the model of semantic paths

    Alexander Andrason


    Full Text Available The present paper demonstrates that insights from the affordances perspective can contribute to developing a more comprehensive model of grammaticalization. The authors argue that the grammaticalization process is afforded differently depending on the values of three contributing parameters: the factor (schematized as a qualitative-quantitative map or a wave of a gram, environment (understood as the structure of the stream along which the gram travels, and actor (narrowed to certain cognitive-epistemological capacities of the users, in particular to the fact of being a native speaker. By relating grammaticalization to these three parameters and by connecting it to the theory of optimization, the proposed model offers a better approximation to realistic cases of grammaticalization: The actor and environment are overtly incorporated into the model and divergences from canonical grammaticalization paths are both tolerated and explicable.

  8. Determinants of orthodontic treatment need and demand: a cross-sectional path model study.

    Taghavi Bayat, Jari; Huggare, Jan; Mohlin, Bengt; Akrami, Nazar


    To put forward a model predicting orthodontic treatment need and demand. Furthermore, to explore how much of the variance in treatment demand could be explained by a set of self-assessed measures, and how these measures relate to professionally assessed treatment need. One hundred and fifty adolescents, aged 13 years, completed a questionnaire which included a set of self-assessed measures dealing with self-esteem, such as dental and global self-esteem, various aspects of malocclusion, such as perceived malocclusion and perceived functional limitation, and treatment demand. Treatment need was assessed by Dental Health Component of the Index of Orthodontic Treatment Need grading. Path analysis was used to examine the relations between the measures and if they could predict treatment need and demand. The measures proved to be reliable and inter-correlated. Path analysis revealed that the proposed model had good fit to the data, providing a test of the unique effect of all included measures on treatment need and demand. The model explained 33% of the variance in treatment demand and 22% of the variance in treatment need. The specific age group could affect the generalizability of the findings. Moreover, although showing good fit to data, the final model is based on a combination of theoretical reasoning and semi-explorative approach. The proposed model displays the unique effect of each included measure on treatment need and demand, explaining a large proportion of the variance in perceived treatment demand and professionally assessed treatment need. The model would hopefully lead to improved and more cost-efficient predictions of treatment need and demand. © The Author 2016. Published by Oxford University Press on behalf of the European Orthodontic Society. All rights reserved. For permissions, please email:

  9. A H-Infinity Control for Path Tracking with Fuzzy Hyperbolic Tangent Model

    Guangsi Shi


    Full Text Available To achieve the goal of driver-less underground mining truck, a fuzzy hyperbolic tangent model is established for path tracking on an underground articulated mining truck. Firstly, the sample data of parameters are collected by the driver controlling articulated vehicle at a speed of 3 m/s, including both the lateral position deviation and the variation of heading angle deviation. Then, according to the improved adaptive BP neural network model and deriving formula of mediation rate of error estimator by the method of Cauchy robust, the weights are identified. Finally, H-infinity control controller is designed to control steering angle. The results of hardware-in-the-loop simulation show that lateral position deviation, heading angle deviation, and steering angle of the vehicle can be controlled, respectively, at 0.024 m, 0.08 rad, and 0.21 rad. All the deviations are asymptotically stable, and error control is in less than 2%. The method is demonstrated to be effective and reliable in path tracking for the underground vehicles.

  10. Chinese Culture, Homosexuality Stigma, Social Support and Condom Use: A Path Analytic Model.

    Liu, Hongjie; Feng, Tiejian; Ha, Toan; Liu, Hui; Cai, Yumao; Liu, Xiaoli; Li, Jian


    PURPOSE: The objective of this study was to examine the interrelationships among individualism, collectivism, homosexuality-related stigma, social support, and condom use among Chinese homosexual men. METHODS: A cross-sectional study using the respondent-driven sampling approach was conducted among 351 participants in Shenzhen, China. Path analytic modeling was used to analyze the interrelationships. RESULTS: The results of path analytic modeling document the following statistically significant associations with regard to homosexuality: (1) higher levels of vertical collectivism were associated with higher levels of public stigma [β (standardized coefficient) = 0.12] and self stigma (β = 0.12); (2) higher levels of vertical individualism were associated with higher levels self stigma (β = 0.18); (3) higher levels of horizontal individualism were associated with higher levels of public stigma (β = 0.12); (4) higher levels of self stigma were associated with higher levels of social support from sexual partners (β = 0.12); and (5) lower levels of public stigma were associated with consistent condom use (β = -0.19). CONCLUSIONS: The findings enhance our understanding of how individualist and collectivist cultures influence the development of homosexuality-related stigma, which in turn may affect individuals' decisions to engage in HIV-protective practices and seek social support. Accordingly, the development of HIV interventions for homosexual men in China should take the characteristics of Chinese culture into consideration.

  11. Step out the Paradox of Livable City Studies:Conceptual Model and Path Choice


    Based on a comparative analysis on the concepts and standards of livable city in China and abroad,the paper creates a conceptual model and a fundamental formula for livable city development with economic development as the foundation,and the social and cultural conditions,the ecological status,and the city governance as three pillars,so as to provide a theoretical explanation for the two paradoxes of livable city.The paper suggests that China should choose Path C,which combines economic development with city livability.It also analyzes the development rules of livable city under Path C,and talks about the fundamental ideas of livable city construction under the current circumstances in China.In the end,the paper puts forward related planning strategies in terms of spatial structure,ecological environment,cultural construction,transportation system,and housing system,in order to establish a livable city development model that is suitable for China’s practical conditions.

  12. Direct adaptive feedforward compensation of narrowband disturbances without explicit identification of the secondary path model

    Zech, Philipp; Lato, Victorio; Rinderknecht, Stephan


    The effectiveness of common algorithms for feedforward compensation of narrowband disturbance depends mainly on the model quality. To avoid this dependency several direct adaptive control algorithms without explicitly identified secondary path models have been developed over the last years. However an overview of their properties and a comparison of their performances in a standardized benchmark is still lacking. In this paper the three most promising algorithms are modified for narrowband feedforward vibration control for the use in rotating machinery. As in this application the reference signal is generated using the frequency measurement from a speed sensor it can be assumed that there is no coupling between reference measurement and the secondary path. First the algorithms are tested in simulation, then they are implemented on a test rig for active vibration control of unbalance induced rotor vibration. In simulation as well as for the test rig the performances of the algorithms are compared to each other. Advantages and drawbacks of the algorithms are discussed and practical instructions for implementation are given. The work is intended to serve as starting point and motivation for future research in this field of study.

  13. Geographic Information System-Allocation Model for Forest Path: A Case Study in Ayer Hitam Forest Reserve, Malaysia

    I. M. Hasmadi


    Full Text Available Problem statement: Forest road planning requires a host of information, particularly the availability of spatial and non-spatial data. The requirement of a planning system or tools to gather, integrate and manipulate all data is essential. The ability of Geographic Information System (GIS to integrate such massive information and develop a spatial model of earth features will lead to time and cost reduction and allows analysis of spatial problems more effective than the traditional method. Approach: The objective of this study was to test the potential of GIS in modeling forest road allocation in Ayer Hitam Forest Reserve (AHFR, Selangor, Malaysia. This study is also to compare a road profile (new path generated from GIS approach (new path with existing forest road and allocates the best road path for compartment 2 and 14. Data from digital topographic map was used to generate slope class, elevation class, direction and distance. New road paths were determined using spatial analyst. Several module or technique that used were cost weight, reclassify, raster calculator and shortest path modeling. Results: Results showed that road path generated from GIS technique was shorter and avoid more unnecessary slope and elevation. Road profiles such as elevation, slope and length were analyzed and discussed. Conclusion: The result clearly revealed that GIS has strength and played a vital role in modeling forest road allocation effectively and reduced time consuming.

  14. Path sets size, model specification, or model estimation: Which one matters most in predicting stochastic user equilibrium traffic flow?

    Milad Haghani


    Further investigations with respect to the relative importance of STA model estimation (or equivalently, parameter calibration and model specification (or equivalently, error term formulation are also conducted. A paired combinatorial logit (PCL assignment model with an origin–destination-specific-parameter, along with a heuristic method of model estimation (calibration, is proposed. The proposed model cannot only accommodate the correlation between path utilities, but also accounts for the fact that travelling between different origin–destination (O–D pairs can correspond to different levels of stochasticity and choice randomness. Results suggest that the estimation of the stochastic user equilibrium (SUE models can affect the outcome of the flow prediction far more meaningfully than the complexity of the choice model (i.e., model specification.

  15. Population-reaction model and microbial experimental ecosystems for understanding hierarchical dynamics of ecosystems.

    Hosoda, Kazufumi; Tsuda, Soichiro; Kadowaki, Kohmei; Nakamura, Yutaka; Nakano, Tadashi; Ishii, Kojiro


    Understanding ecosystem dynamics is crucial as contemporary human societies face ecosystem degradation. One of the challenges that needs to be recognized is the complex hierarchical dynamics. Conventional dynamic models in ecology often represent only the population level and have yet to include the dynamics of the sub-organism level, which makes an ecosystem a complex adaptive system that shows characteristic behaviors such as resilience and regime shifts. The neglect of the sub-organism level in the conventional dynamic models would be because integrating multiple hierarchical levels makes the models unnecessarily complex unless supporting experimental data are present. Now that large amounts of molecular and ecological data are increasingly accessible in microbial experimental ecosystems, it is worthwhile to tackle the questions of their complex hierarchical dynamics. Here, we propose an approach that combines microbial experimental ecosystems and a hierarchical dynamic model named population-reaction model. We present a simple microbial experimental ecosystem as an example and show how the system can be analyzed by a population-reaction model. We also show that population-reaction models can be applied to various ecological concepts, such as predator-prey interactions, climate change, evolution, and stability of diversity. Our approach will reveal a path to the general understanding of various ecosystems and organisms. Copyright © 2015 The Authors. Published by Elsevier Ireland Ltd.. All rights reserved.

  16. Environmental influences on fruit and vegetable intake: results from a path analytic model.

    Liese, Angela D; Bell, Bethany A; Barnes, Timothy L; Colabianchi, Natalie; Hibbert, James D; Blake, Christine E; Freedman, Darcy A


    Fruit and vegetable (F&V) intake is influenced by behavioural and environmental factors, but these have rarely been assessed simultaneously. We aimed to quantify the relative influence of supermarket availability, perceptions of the food environment and shopping behaviour on F&V intake. A cross-sectional study. Eight counties in South Carolina, USA, with verified locations of all supermarkets. A telephone survey of 831 household food shoppers ascertained F&V intake with a seventeen-item screener, primary food store location, shopping frequency and perceptions of healthy food availability, and supermarket availability was calculated with a geographic information system. Path analysis was conducted. We report standardized beta coefficients on paths significant at the 0·05 level. Frequency of grocery shopping at primary food store (β = 0·11) was the only factor exerting an independent, statistically significant direct effect on F&V intake. Supermarket availability was significantly associated with distance to utilized food store (β = -0·24) and shopping frequency (β = 0·10). Increased supermarket availability was significantly and positively related to perceived healthy food availability in the neighbourhood (β = 0·18) and ease of shopping access (β = 0·09). Collectively considering all model paths linked to perceived availability of healthy foods, this measure was the only other factor to have a significant total effect on F&V intake. While the majority of the literature to date has suggested an independent and important role of supermarket availability for F&V intake, our study found only indirect effects of supermarket availability and suggests that food shopping frequency and perceptions of healthy food availability are two integral components of a network of influences on F&V intake.

  17. A quantative evaluation of the reformulated 1996 path-goal theory of work unit leadership via structural equation modelling

    Howieson, William B


    In 1996, Professor Robert J House published a reformulated Path-Goal Theory of Work Unit Leadership, based on his earlier 1971 and 1974 theories. Path-goal leadership attempts to explain the impact that leader behaviour has on subordinate motivation, satisfaction and performance. The aim of this context-specific study is to evaluate this reformulated ‘1996 Theory’ via Structural Equation Modelling with engineers from the Royal Air Force as the primary data source. This th...

  18. The dissociative chemisorption of methane on Ni(100) and Ni(111): classical and quantum studies based on the reaction path Hamiltonian.

    Mastromatteo, Michael; Jackson, Bret


    Electronic structure methods based on density functional theory are used to construct a reaction path Hamiltonian for CH4 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 vibrational 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.


    Grove, David B.; Stollenwerk, Kenneth G.


    Recent literature concerning the modeling of chemical reactions during transport in ground water is examined with emphasis on sorption reactions. The theory of transport and reactions in porous media has been well documented. Numerous equations have been developed from this theory, to provide both continuous and sequential or multistep models, with the water phase considered for both mobile and immobile phases. Chemical reactions can be either equilibrium or non-equilibrium, and can be quantified in linear or non-linear mathematical forms. Non-equilibrium reactions can be separated into kinetic and diffusional rate-limiting mechanisms. Solutions to the equations are available by either analytical expressions or numerical techniques. Saturated and unsaturated batch, column, and field studies are discussed with one-dimensional, laboratory-column experiments predominating. A summary table is presented that references the various kinds of models studied and their applications in predicting chemical concentrations in ground waters.

  20. Optimal investment paths for future renewable based energy systems - Using the optimisation model Balmorel

    Karlsson, Kenneth Bernard; Meibom, Peter


    that with an oil price at 100 $/barrel, a CO2 price at40 €/ton and the assumed penetration of hydrogen in the transport sector, it is economically optimal to cover more than 95% of the primary energy consumption for electricity and district heat by renewables in 2050. When the transport sector is converted......This paper investigates a possible long term investment path for the Nordic energy system focussing on renewable energy in the supply sector and on hydrogen as the main fuel for transportation, covering up to 70% of all transport in 2050. The optimisation model Balmorel [Ravn H, et al. Balmorel......: A model for analyses of the electricity and CHP markets in the Baltic Sea Region. 〈〉; 2001. [1

  1. Characterization of particle deposition in a lung model using an individual path

    Ferrera C.


    Full Text Available Suspended particles can cause a wide range of chronic respiratory illnesses such as asthma and chronic obstructive pulmonary diseases, as well as worsening heart conditions and other conditions. To know the particle depositions in realistic models of the human respiratory system is fundamental to prevent these diseases. The main objective of this work is to study the lung deposition of inhaled particles through a numerical model using UDF (User Defined Function to impose the boundary conditions in the truncated airways. For each generation, this UDF puts the values of velocity profile of the flow path to symmetrical truncated outlet. The flow rates tested were 10, 30 and 60 ℓ/min, with a range of particles between 0.1 µm and 20 µm.

  2. Antenatal depressive symptoms and subjective birth experience in association with postpartum depressive symptoms and acute stress reaction in mothers and fathers: A longitudinal path analysis.

    Gürber, Susanne; Baumeler, Luzia; Grob, Alexander; Surbek, Daniel; Stadlmayr, Werner


    Postpartum depressive symptoms (PDS) and acute stress reactions (ASR) after childbirth are frequently documented in mothers, but research is scarce in fathers. In a longitudinal path analysis, the interplay of depressive symptoms in pregnancy and the subjective childbirth experience of mothers and fathers are examined with regard to the development of PDS and ASR postpartum. One hundred eighty nine expectant couples were recruited between August 2006 and September 2009. They completed the Edinburgh Postnatal Depression Scale (EPDS) in the last trimester of pregnancy. In the first week postpartum, they answered the Salmon's Item List (subjective birth experience), and four weeks after birth the EPDS and the Impact of Event Scale - revised (IES-r). The data were evaluated in a longitudinal path analysis. Compared with fathers, mothers reported more depressive symptoms (pregnancy: pexperience' (p0.10), but moderately correlated four weeks after birth (r=0.387, pexperience were independently predictive of PDS and ASR after childbirth in mothers and fathers controlling for age, mode of delivery, parity, epidural anaesthesia, infant gender and birth weight. Antenatal depressive symptoms were related to subjective childbirth experience only in fathers. Parental prenatal depressive symptoms and subjective birth experience are important predictors of postnatal psychological adjustment in mothers and fathers. Copyright © 2017. Published by Elsevier B.V.

  3. Abundances in Astrophysical Environments: Reaction Network Simulations with Reaction Rates from Many-nucleon Modeling

    Amason, Charlee; Dreyfuss, Alison; Launey, Kristina; Draayer, Jerry


    We use the ab initio (first-principle) symmetry-adapted no-core shell model (SA-NCSM) to calculate reaction rates of significance to type I X-ray burst nucleosynthesis. We consider the 18O(p,γ)19F reaction, which may influence the production of fluorine, as well as the 16O(α,γ)20Ne reaction, which is key to understanding the production of heavier elements in the universe. Results are compared to those obtained in the no-core sympletic shell model (NCSpM) with a schematic interaction. We discuss how these reaction rates affect the relevant elemental abundances. We thank the NSF for supporting this work through the REU Site in Physics & Astronomy (NSF grant #1560212) at Louisiana State University. This work was also supported by the U.S. NSF (OCI-0904874, ACI -1516338) and the U.S. DOE (DE-SC0005248).

  4. Musculoskeletal model-based control interface mimics physiologic hand dynamics during path tracing task

    Crouch, Dustin L.; (Helen Huang, He


    Objective. We investigated the feasibility of a novel, customizable, simplified EMG-driven musculoskeletal model for estimating coordinated hand and wrist motions during a real-time path tracing task. Approach. A two-degree-of-freedom computational musculoskeletal model was implemented for real-time EMG-driven control of a stick figure hand displayed on a computer screen. After 5-10 minutes of undirected practice, subjects were given three attempts to trace 10 straight paths, one at a time, with the fingertip of the virtual hand. Able-bodied subjects completed the task on two separate test days. Main results. Across subjects and test days, there was a significant linear relationship between log-transformed measures of accuracy and speed (Pearson’s r  =  0.25, p  motor control patterns were not accustomed to the multi-joint dynamics of the wrist and hand, possibly as a result of post-amputation cortical plasticity, disuse, or sensory deficits. Significance. To our knowledge, our study is one of very few that have demonstrated the real-time simultaneous control of multi-joint movements, especially wrist and finger movements, using an EMG-driven musculoskeletal model, which differs from the many data-driven algorithms that dominate the literature on EMG-driven prosthesis control. Real-time control was achieved with very little training and simple, quick (~15 s) calibration. Thus, our model is potentially a practical and effective control platform for multifunctional myoelectric prostheses that could restore more life-like hand function for individuals with upper limb amputation.

  5. Analytic solutions for seismic travel time and ray path geometry through simple velocity models.

    Ballard, Sanford


    The geometry of ray paths through realistic Earth models can be extremely complex due to the vertical and lateral heterogeneity of the velocity distribution within the models. Calculation of high fidelity ray paths and travel times through these models generally involves sophisticated algorithms that require significant assumptions and approximations. To test such algorithms it is desirable to have available analytic solutions for the geometry and travel time of rays through simpler velocity distributions against which the more complex algorithms can be compared. Also, in situations where computational performance requirements prohibit implementation of full 3D algorithms, it may be necessary to accept the accuracy limitations of analytic solutions in order to compute solutions that satisfy those requirements. Analytic solutions are described for the geometry and travel time of infinite frequency rays through radially symmetric 1D Earth models characterized by an inner sphere where the velocity distribution is given by the function V (r) = A-Br{sup 2}, optionally surrounded by some number of spherical shells of constant velocity. The mathematical basis of the calculations is described, sample calculations are presented, and results are compared to the Taup Toolkit of Crotwell et al. (1999). These solutions are useful for evaluating the fidelity of sophisticated 3D travel time calculators and in situations where performance requirements preclude the use of more computationally intensive calculators. It should be noted that most of the solutions presented are only quasi-analytic. Exact, closed form equations are derived but computation of solutions to specific problems generally require application of numerical integration or root finding techniques, which, while approximations, can be calculated to very high accuracy. Tolerances are set in the numerical algorithms such that computed travel time accuracies are better than 1 microsecond.

  6. Concurrent Phenomena at the Reaction Path of the SN2 Reaction CH3Cl + F−. Information Planes and Statistical Complexity Analysis

    Moyocoyani Molina-Espíritu


    Full Text Available An information-theoretical complexity analysis of the SN2 exchange reaction for CH3Cl + F− is performed in both position and momentum spaces by means of the following composite functionals of the one-particle density: D-L and I-J planes and Fisher-Shannon’s (FS and López-Ruiz-Mancini-Calbet (LMC shape complexities. It was found that all the chemical concepts traditionally assigned to elementary reactions such as the breaking/forming regions (B-B/F, the charge transfer/reorganization and the charge repulsion can be unraveled from the phenomenological analysis performed in this study through aspects of localizability, uniformity and disorder associated with the information-theoretical functionals. In contrast, no energy-based functionals can reveal the above mentioned chemical concepts. In addition, it is found that the TS critical point for this reaction does not show any chemical meaning (other than the barrier height as compared with the concurrent processes revealed by the information-theoretical analysis. Instead, it is apparent from this study that a maximum delocalized state could be identified in the transition region which is associated to the charge transfer process as a new concurrent phenomenon associated with the charge transfer region (CT for the ion-complex is identified. Finally it is discussed why most of the chemical features of interest (e.g., CT, B-B/F are only revealed when some information-theoretic properties are taken into account, such as localizability, uniformity and disorder.


    Pfefferle, Susan G; Spitznagel, Edward L


    OBJECTIVE: This observational study explores pathways towards any past year use of child mental health services. METHODS: Data from the 2002 National Survey of American Families were used to explore the relationship between past month maternal mental health and past year child mental health services use. Observations were limited to the 8072 most knowledgeable adults who were the mothers of target children aged 6-11. Logistic regressions were performed to determine the odds of any child mental health service use followed by path analyses using Maximum Likelihood estimation with robust standard errors. RESULTS: Multiple factors were associated with odds of any child mental health service use. In the path analytic model poor past month maternal mental health was associated with increased aggravation which in turn was associated with increased use of mental health visits. Negative child behaviors as reported by the mother were also associated with increased maternal aggravation and increased service use. CONCLUSIONS: Parental perception of child behaviors influences treatment seeking, both directly and indirectly through parental aggravation. Parental mental health influences tolerance for child behaviors. Findings are consistent with other studies. Interventions should address the entire family and their psychosocial circumstances through collaboration between multiple service sectors.

  8. Dynamic Modeling and Soil Mechanics for Path Planning of the Mars Exploration Rovers

    Trease, Brian; Arvidson, Raymond; Lindemann, Randel; Bennett, Keith; Zhou, Feng; Iagnemma, Karl; Senatore, Carmine; Van Dyke, Lauren


    To help minimize risk of high sinkage and slippage during drives and to better understand soil properties and rover terramechanics from drive data, a multidisciplinary team was formed under the Mars Exploration Rover (MER) project to develop and utilize dynamic computer-based models for rover drives over realistic terrains. The resulting tool, named ARTEMIS (Adams-based Rover Terramechanics and Mobility Interaction Simulator), consists of the dynamic model, a library of terramechanics subroutines, and the high-resolution digital elevation maps of the Mars surface. A 200-element model of the rovers was developed and validated for drop tests before launch, using MSC-Adams dynamic modeling software. Newly modeled terrain-rover interactions include the rut-formation effect of deformable soils, using the classical Bekker-Wong implementation of compaction resistances and bull-dozing effects. The paper presents the details and implementation of the model with two case studies based on actual MER telemetry data. In its final form, ARTEMIS will be used in a predictive manner to assess terrain navigability and will become part of the overall effort in path planning and navigation for both Martian and lunar rovers.

  9. Characterization of the Minimum Energy Paths for the Ring Closure Reactions of C4H3 with Acetylene

    Walch, Stephen P.


    The ring closure reaction of C4H3 with acetylene to give phenyl radical is one proposed mechanism for the formation of the first aromatic ring in hydrocarbon combustion. There are two low-lying isomers of C4H3; 1-dehydro-buta-l-ene-3-yne (n-C4H3) and 2-dehydro-buta-l-ene-3-yne (iso-C4H3). It has been proposed that only n-C4H3 reacts with acetylene to give phenyl radical, and since iso-C4H3 is more stable than n-C4H3, formation of phenyl radical by this mechanism is unlikely. We report restricted Hartree-Fock (RHF) plus singles and doubles configuration interaction calculations with a Davidson's correction (RHF+1+2+Q) using the Dunning correlation consistent polarized valence double zeta basis set (cc-pVDZ) for stationary point structures along the reaction pathway for the reactions of n-C4H3 and iso-C4H3 with acetylene. n-C4H3 plus acetylene (9.4) has a small entrance channel barrier (17.7) (all energetics in parentheses are in kcal/mol with respect to iso-C4H3 plus acetylene) and the subsequent closure steps leading to phenyl radical (-91.9) are downhill with respect to the entrance channel barrier. Iso-C4H3 Plus acetylene also has an entrance channel barrier (14.9) and there is a downhill pathway to 1-dehydro-fulvene (-55.0). 1-dehydro-fulvene can rearrange to 6-dehydro-fulvene (-60.3) by a 1,3-hydrogen shift over a barrier (4.0), which is still below the entrance channel barrier, from which rearrangement to phenyl radical can occur by a downhill pathway. Thus, both n-C4H3 and iso-C4H3 can react with acetylene to give phenyl radical with small barriers.

  10. Formal modeling of a system of chemical reactions under uncertainty.

    Ghosh, Krishnendu; Schlipf, John


    We describe a novel formalism representing a system of chemical reactions, with imprecise rates of reactions and concentrations of chemicals, and describe a model reduction method, pruning, based on the chemical properties. We present two algorithms, midpoint approximation and interval approximation, for construction of efficient model abstractions with uncertainty in data. We evaluate computational feasibility by posing queries in computation tree logic (CTL) on a prototype of extracellular-signal-regulated kinase (ERK) pathway.

  11. Path Dependency

    Mark Setterfield


    Path dependency is defined, and three different specific concepts of path dependency – cumulative causation, lock in, and hysteresis – are analyzed. The relationships between path dependency and equilibrium, and path dependency and fundamental uncertainty are also discussed. Finally, a typology of dynamical systems is developed to clarify these relationships.

  12. 甲烷等离子体转化合成碳二烃反应过程和过渡态理论%Theoretical Study of Reaction Paths and Transition States on Conversion Methane into C2 Hydrocarbons Through Plasma

    王保伟; 杨恩翠; 许根慧; 郝金库


    The direct synthesis of C2 hydrocarbons (ethylene, acetylene and ethane) from methane is one of the most important task in C1 chemistry. Higher conversion of methane and selectivity to C2 hydrocarbons can be realized through plasma reaction. In order to explore the reaction process and mechanism, the possible reaction paths (1)-(4) were proposed on coupling reaction of methane through plasma and studied theoretically using semi-PM3 method [PM3 is parametcrization method of modified neglect of diatomic overlap (MNDO)] including determining the transition state, calculating the activation energy and thermodynamic state functions and analyzing the bond order and intrinsic reaction coordinate. The reaction heat results indicate that the reactions (2) and (4) are exothermic,while reactions of (1) and (3) are endothermic. The activation energy results show that activation energy for reactions (1) and (2) was much lower than that of reaction paths (3) and (4). Therefore, paths (1) and (2) is the favorable reaction path energetically. More interestingly by comparing the intrinsic reaction coordinated (IRC) of the reaction paths (1) and (2), it is found that the variations of bond lengths in reaction path (1) has a crucial effect on the potential energy, while in reaction path (2), the adjustment of the system geometry also contributes to the whole potential energy of the system.

  13. Principle Generalized Net Model of a Human Stress Reaction

    Anthony Shannon


    Full Text Available The present study was aimed at investigating the mechanism of a human stress reaction by means of Generalized Nets (GNs. A principle GN-model of the main structures, organs and systems of the human body taking part in the acute and chronic reaction of the organism to a stress stimulus is generated. A possible application of the GN-model of the human stress reaction for testing the effect of known or newly synthesized pharmacological products as well as of food supplements is discussed.

  14. A Path Analysis of Educator Perceptions of Open Educational Resources Using the Technology Acceptance Model

    Hope Kelly


    Full Text Available Open educational resources (OER are making their way into a variety of educational contexts from formal lesson planning to just in time learning. Educators and training professionals have been recognized as an important audience for these materials. The concepts of self-efficacy and outcome judgment from social cognitive learning theory serve as theoretical constructs to measure educator perceptions of OER. This study uses a path analysis, based on the technology acceptance model, to understand adoption of these resources by this audience with a particular emphasis on self-efficacy. Among the participants, three main groups were identified: K-12 educators, higher education professionals, and those involved in workplace training. A discriminant function analysis found that K-12 educators stood out as finding OER relevant to improving their practice. Recommendations are made in regards to an emphasis on easy to use designs to improve application self-efficacy of OER and instructional messaging for future K-12 educators.

  15. Modeling Electric Double-Layers Including Chemical Reaction Effects

    Paz-Garcia, Juan Manuel; Johannesson, Björn; Ottosen, Lisbeth M.


    A physicochemical and numerical model for the transient formation of an electric double-layer between an electrolyte and a chemically-active flat surface is presented, based on a finite elements integration of the nonlinear Nernst-Planck-Poisson model including chemical reactions. The model works...

  16. Turing patterns in a reaction-diffusion model with the Degn-Harrison reaction scheme

    Li, Shanbing; Wu, Jianhua; Dong, Yaying


    In this paper, we consider a reaction-diffusion model with Degn-Harrison reaction scheme. Some fundamental analytic properties of nonconstant positive solutions are first investigated. We next study the stability of constant steady-state solution to both ODE and PDE models. Our result also indicates that if either the size of the reactor or the effective diffusion rate is large enough, then the system does not admit nonconstant positive solutions. Finally, we establish the global structure of steady-state bifurcations from simple eigenvalues by bifurcation theory and the local structure of the steady-state bifurcations from double eigenvalues by the techniques of space decomposition and implicit function theorem.

  17. The shortest time and/or the shortest path strategies in a CA FF pedestrian dynamics model

    Kirik, Ekaterina; Krouglov, Dmitriy


    This paper deals with a mathematical model of a pedestrian movement. A stochastic cellular automata (CA) approach is used here. The Floor Field (FF) model is a basis model. FF models imply that virtual people follow the shortest path strategy. But people are followed by a strategy of the shortest time as well. This paper is focused on how to mathematically formalize and implement to a model these features of the pedestrian movement. Some results of a simulation are presented.

  18. Investigating the Anticonvulsant Effects of Repetitive Transcranial Magnetic Stimulation on Perforant Path Kindling Model in Rats

    Ali Yadollahpour


    Full Text Available Background: Almost 20% of epileptics are drug resistant. Studies have shown that low frequency repetitive transcranial magnetic stimulation (rTMS is with therapeutic effects on epilepsy-affected laboratory models. Anticonvulsant effects of rTMS depend on several parameters among which radiation frequency is the most important one. In this study, the therapeutic impacts of 1 and 2 Hz rTMS on convulsing parameters in epileptic model of electrical kindling stimulation of the perforant path were investigated. Materials and Methods: In this experimental study 21 rats were randomly divided into three groups, namely ‘1 Hz treatment group’ and ‘2 Hz treatment group’ and ‘kindling group’. The kindling group only received kindling stimulations for seven days. One Hz and 2 Hz frequency treatment groups received maximally 5 min rTMS after termination of kindling stimulation per day for a week. Stimulation and stability electrodes had been placed, in turn, on perforant path and dentate gyrus. For quantifying the duration of the subsequent discharge waves, two-way ANOVA test and Bonferroni post-test were employed. In addition, for quantifying the convulsive behaviors, Kruskal-Wallis and the Mann-Whitney U tests were used. Results: The results showed that 1 Hz and 2 Hz frequency rTMS have considerable inhibitory impact on the development of convulsive phases. Anticonvulsive effect was observed from the first day after rTMS was undertaken. In addition, the animals did not show fourth and fifth convulsive stages, and a significant reduction was evident in their recorded peak discharge waves compared with kindle group. Conclusion: Low frequency rTMS possesses significant anticonvulsive effects which depend upon sTMS stimulation frequency.

  19. Breakup reaction models for two- and three-cluster projectiles

    Baye, D


    Breakup reactions are one of the main tools for the study of exotic nuclei, and in particular of their continuum. In order to get valuable information from measurements, a precise reaction model coupled to a fair description of the projectile is needed. We assume that the projectile initially possesses a cluster structure, which is revealed by the dissociation process. This structure is described by a few-body Hamiltonian involving effective forces between the clusters. Within this assumption, we review various reaction models. In semiclassical models, the projectile-target relative motion is described by a classical trajectory and the reaction properties are deduced by solving a time-dependent Schroedinger equation. We then describe the principle and variants of the eikonal approximation: the dynamical eikonal approximation, the standard eikonal approximation, and a corrected version avoiding Coulomb divergence. Finally, we present the continuum-discretized coupled-channel method (CDCC), in which the Schroed...

  20. A comparison of the classroom dynamics of a problem-solving and traditional laboratory model of instruction using path analysis

    Pizzini, Edward L.; Shepardson, Daniel P.

    The classroom dynamics (class setting, lesson structure, student interactions, and student behaviors) of a traditional laboratory and a problem-solving Search, Solve, Create, and Share (SSCS) model of instruction were compared using path analysis. Class setting was based on small-group/large-group settings. Lesson structure variables were problem finding/refining, research designing, data collecting, data analyzing, and evaluating. The student-student interactions variable was determined by student-student responding, student-student initiating, and student (self-) interaction; while the teacher-student interaction variable was based on teacher-student initiating and teacher-student responding. The dependent variables of student behavior consisted of attending, responding, following, soliciting, and giving. A causal model was hypothesized for both instructional models based on the independent and dependent variables. The hypothesized causal model was tested using path-analysis procedures described by Pedhazur (1982). The hypothesized causal models were adjusted based on path coefficients with levels of significance greater than p = 0.05. While the descriptive data indicated a similarity in the classroom dynamics of the two instructional models, path analysis indicated a difference in the classroom dynamics. In the traditional laboratory model, student behaviors did not correlate to lesson structure, class setting, or student interactions, whereas in the SSCS problem-solving model student behaviors correlated to aspects of the lesson structure, class setting, and student interactions.

  1. A Prediction Study of Path Loss Models from 2-73.5 GHz in an Urban-Macro Environment

    Thomas, Timothy; Rybakowski, Marcin; Sun, Shu


    It is becoming clear that 5G wireless systems will encompass frequencies from around 500 MHz all the way to around 100 GHz. To adequately assess the performance of 5G systems in these different bands, path loss (PL) models will need to be developed across this wide frequency range. The PL models ...

  2. Regimes of chemical reaction waves initiated by nonuniform initial conditions for detailed chemical reaction models.

    Liberman, M A; Kiverin, A D; Ivanov, M F


    Regimes of chemical reaction wave propagation initiated by initial temperature nonuniformity in gaseous mixtures, whose chemistry is governed by chain-branching kinetics, are studied using a multispecies transport model and a detailed chemical model. Possible regimes of reaction wave propagation are identified for stoichiometric hydrogen-oxygen and hydrogen-air mixtures in a wide range of initial pressures and temperature levels, depending on the initial non-uniformity steepness. The limits of the regimes of reaction wave propagation depend upon the values of the spontaneous wave speed and the characteristic velocities of the problem. It is shown that one-step kinetics cannot reproduce either quantitative neither qualitative features of the ignition process in real gaseous mixtures because the difference between the induction time and the time when the exothermic reaction begins significantly affects the ignition, evolution, and coupling of the spontaneous reaction wave and the pressure wave, especially at lower temperatures. We show that all the regimes initiated by the temperature gradient occur for much shallower temperature gradients than predicted by a one-step model. The difference is very large for lower initial pressures and for slowly reacting mixtures. In this way the paper provides an answer to questions, important in practice, about the ignition energy, its distribution, and the scale of the initial nonuniformity required for ignition in one or another regime of combustion wave propagation.

  3. Biomass torrefaction: modeling of reaction thermochemistry.

    Bates, Richard B; Ghoniem, Ahmed F


    Based on the evolution of volatile and solid products predicted by a previous model for willow torrefaction (Bates and Ghoniem, 2012) a thermochemical model has been developed to describe their thermal, chemical, and physical properties as well as the rates of heat release. The first stage of torrefaction, associated with hemicellulose decomposition, is exothermic releasing between 40 and 280 kJ/kginitial. The second stage is associated with the decomposition of the remaining lignocellulosic components, completes over a longer period, and is predicted to be either endothermic or exothermic depending on the temperature and assumed solid properties. Cumulative heat release increases with the degree of torrefaction quantified by the mass loss. The rate of mass loss and rate of heat release increase with higher temperatures. The higher heating value of volatiles produced during torrefaction was estimated to be between 4.4 and 16 MJ/kg increasing with the level of mass loss.

  4. Biogeochemical Transport and Reaction Model (BeTR) v1


    The Biogeochemical Transport and Reaction Model (BeTR) is a F90 code that enables reactive transport modeling in land modules of earth system models (e.g. CESM, ACME). The code adopts the Objective-Oriented-Design, and allows users to plug in their own biogeochemical (BGC) formulations/codes, and compare them to other existing BGC codes in those ESMs. The code takes information of soil physics variables, such as variables, such as temperature, moisture, soil density profile; water flow, etc., from a land model to track the movement of different chemicals in presence of biogeochemical reactions.

  5. Testing a model of L2 communication among Iranian EFL learners: A Path Analysis Framework

    Nasser Fallah


    Full Text Available Using willingness to communicate (WTC and socio-educational models as a framework, the present study aimed at examining WTC in English and its underlying variables in a sample of 372 Iranian non-English major EFL learners. The data were collected through self-reported questionnaires. Path analysis framework using the Amos Program with maximum likelihood estimation was also utilized to examine the hypothesized model and the potential relationships between the variables. The final model showed a very good fit to the data. The results of structural equation modeling revealed that self-perceived communication competence (SPCC, international posture and motivation were significant predictors of L2WTC. The findings also showed that L2 communication anxiety (CA, motivation, personality trait of agreeableness and teacher immediacy could exert indirect effects on L2WTC. Furthermore, each of teacher immediacy and agreeableness variables predicted both international posture and CA among the EFL learners. Following these findings, potential factors affecting learners WTC should receive sufficient attention by teachers, administrators and learners alike. By adopting more immediacy behaviors, EFL teachers can also establish relaxing and supportive classroom climate and lower the learners’ affective filter. In such an atmosphere learners are more emotionally secured, suffer less communication apprehension, perceive themselves to be more proficient and motivated, obtain promoted international posture by forming realistic attitudes toward different cultures, and consequently become more willing to communicate in English.

  6. Pursuit eye-movements in curve driving differentiate between future path and tangent point models.

    Otto Lappi

    Full Text Available For nearly 20 years, looking at the tangent point on the road edge has been prominent in models of visual orientation in curve driving. It is the most common interpretation of the commonly observed pattern of car drivers looking through a bend, or at the apex of the curve. Indeed, in the visual science literature, visual orientation towards the inside of a bend has become known as "tangent point orientation". Yet, it remains to be empirically established whether it is the tangent point the drivers are looking at, or whether some other reference point on the road surface, or several reference points, are being targeted in addition to, or instead of, the tangent point. Recently discovered optokinetic pursuit eye-movements during curve driving can provide complementary evidence over and above traditional gaze-position measures. This paper presents the first detailed quantitative analysis of pursuit eye movements elicited by curvilinear optic flow in real driving. The data implicates the far zone beyond the tangent point as an important gaze target area during steady-state cornering. This is in line with the future path steering models, but difficult to reconcile with any pure tangent point steering model. We conclude that the tangent point steering models do not provide a general explanation of eye movement and steering during a curve driving sequence and cannot be considered uncritically as the default interpretation when the gaze position distribution is observed to be situated in the region of the curve apex.

  7. Development and validation of a path analytic model of students' performance in chemistry

    Anamuah-Mensah, Jophus; Erickson, Gaalen; Gaskell, Jim

    This article reports the development and validation of an integrated model of performance on a chemical concept - volumetric analysis. From the chemical literature a path-analytic model of performance on volumetric analysis calculation was postulated based on studies utilizing the proportional reasoning schema of Piaget and the Cumulative learning theory of Gagne. This integrated model hypothesized some relationships among the variables: direct proportional reasoning, inverse proportional reasoning, prerequisite concepts (content) and performance on volumetric analysis calculations. This model was postulated for the two groups of students involved in the study - that is those who use algorithms with understanding and those who use algorithms without understanding. Two hundred and sixty-five grade twelve chemistry students in eight schools (14 classes) in the lower mainland of British Columbia, Canada participated fully in the study. With the exception of the test on volumetric analysis calculations all the other tests were administered prior to the teaching of the unit on volumetric analysis. The results of the study indicate that for subjects using algorithms without understanding, their performance on VA problems is not influenced by proportional reasoning strategies while for those who use algorithms with understanding, their performance is influenced by proportional reasoning strategies.

  8. Kinetic model for hydroisomerization reaction of C8-aromatics

    Ouguan XU; Hongye SU; Xiaoming JIN; Jian CHU


    Based on the reported reaction networks, a novel six-component hydroisomerization reaction net-work with a new lumped species including C8-naphthenes and Cs-paraffins is proposed and a kinetic model for a commercial unit is also developed. An empirical catalyst deactivation function is incorporated into the model accounting for the loss in activity because of coke forma-tion on the catalyst surface during the long-term opera-tion. The Runge-Kutta method is used to solve the ordinary differential equations of the model. The reaction kinetic parameters are benchmarked with several sets of balanced plant data and estimated by the differential vari-able metric optimization method (BFGS). The kinetic model is validated by an industrial unit with sets of plant data under different operating conditions and simulation results show a good agreement between the model predic-tions and the plant observations.

  9. Investigation of Prediction Accuracy, Sensitivity, and Parameter Stability of Large-Scale Propagation Path Loss Models for 5G Wireless Communications

    Sun, Shu; Rappaport, Theodore S.; Thomas, Timothy


    This paper compares three candidate large-scale propagation path loss models for use over the entire microwave and millimeter-wave (mmWave) radio spectrum: the alpha–beta–gamma (ABG) model, the close-in (CI) free-space reference distance model, and the CI model with a frequency-weighted path loss...


    LiYanxing; HuXinkang; ShuaiPing; ZhangZhongfu


    The propagation path of satellite signals in the atmosphere is a curve thus it,is very difficult to calculate its flexure correction accurately, a strict calculating expressions has so far not been derived. In this study, the flexure correction of the refraction curve is divided into two parts and their strict calculating expressions are derived. By use of the standard atmospheric model, the accurate flexure correction of the refraction curve is calculated for different zenith distance Z. On this basis, a calculation model is structured. This model is very simple in structure, convenient in use and high in accuracy. When Z is smaller than 85°,the accuracy of the correction exceeds 0.06mm. The flexure correction is basically proportional to tan2Z and increases rapidly with the increase of Z When Z>50°,the correction is smaller than 0.5 mm and can be neglected. When Z>50°, the correction must be made. When Z is 85°, 88° and 89° , the corrections are 198mm, 8.911m and 28.497 km, respectively. The calculation results shows that the correction estimate by Hopfield is correct when Z≤80°, but too small when Z=89°. The expression in this paper is applicable to any satellite.


    Li Yanxing; Hu Xinkang; Shuai Ping; Zhang Zhongfu


    The propagation path of satellite signals in the atmosphere is a curve thus very difficult to calculate its flexure correction accurately, a strict calculating expressions has so far not been derived. In this study, the flexure correction of the refraction curve is divided into two parts and their strict calculating expressions are derived. By use of the standard atmospheric model, the accurate flexure correction of the refraction curve is calculated for different zenith distance Z. On this basis, a calculation model is structured. This model is very simple in structure, convenient in use and high in accuracy. When Z is smaller than 85°, the accuracy of the correction exceeds 0.06 mm. The flexure correction is basically proportional to tan2Z and increases rapidly with the increase of Z When Z>50°,the correction is smaller than 0.5 mm and can be neglected.When Z>50°, the correction must be made. When Z is 85° , 88° and 89° , the corrections are 198mm, 8. 911 m and 28. 497 km, respectively. The calculation results shows that the correction estimate by Hopfield is correct when Z≤80 °, but too small when Z=89°. The expression in this paper is applicable to any satellite.

  12. A path analysis model of factors influencing children's requests for unhealthy foods.

    Pettigrew, Simone; Jongenelis, Michelle; Miller, Caroline; Chapman, Kathy


    Little is known about the complex combination of factors influencing the extent to which children request unhealthy foods from their parents. The aim of this study was to develop a comprehensive model of influencing factors to provide insight into potential methods of reducing these requests. A web panel provider was used to administer a national online survey to a sample of 1302 Australian parent-child dyads (total sample n=2604). Initial univariate analyses identified potential predictors of children's requests for and consumption of unhealthy foods. The identified variables were subsequently incorporated into a path analysis model that included both parents' and children's reports of children's requests for unhealthy foods. The resulting model accounted for a substantial 31% of the variance in parent-reported food request frequency and 27% of the variance in child-reported request frequency. The variable demonstrating the strongest direct association with both parents' and children's reports of request frequency was the frequency of children's current intake of unhealthy foods. Parents' and children's exposure to food advertising and television viewing time were also positively associated with children's unhealthy food requests. The results highlight the need to break the habitual provision of unhealthy foods to avoid a vicious cycle of requests resulting in consumption. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. A Lattice Boltzmann Model for Oscillating Reaction-Diffusion

    Rodríguez-Romo, Suemi; Ibañez-Orozco, Oscar; Sosa-Herrera, Antonio


    A computational algorithm based on the lattice Boltzmann method (LBM) is proposed to model reaction-diffusion systems. In this paper, we focus on how nonlinear chemical oscillators like Belousov-Zhabotinsky (BZ) and the chlorite-iodide-malonic acid (CIMA) reactions can be modeled by LBM and provide with new insight into the nature and applications of oscillating reactions. We use Gaussian pulse initial concentrations of sulfuric acid in different places of a bidimensional reactor and nondiffusive boundary walls. We clearly show how these systems evolve to a chaotic attractor and produce specific pattern images that are portrayed in the reactions trajectory to the corresponding chaotic attractor and can be used in robotic control.

  14. Reaction Networks For Interstellar Chemical Modelling: Improvements and Challenges

    Wakelam, V; Herbst, E; Troe, J; Geppert, W; Linnartz, H; Oberg, K; Roueff, E; Agundez, M; Pernot, P; Cuppen, H M; Loison, J C; Talbi, D


    We survey the current situation regarding chemical modelling of the synthesis of molecules in the interstellar medium. The present state of knowledge concerning the rate coefficients and their uncertainties for the major gas-phase processes -- ion-neutral reactions, neutral-neutral reactions, radiative association, and dissociative recombination -- is reviewed. Emphasis is placed on those reactions that have been identified, by sensitivity analyses, as 'crucial' in determining the predicted abundances of the species observed in the interstellar medium. These sensitivity analyses have been carried out for gas-phase models of three representative, molecule-rich, astronomical sources: the cold dense molecular clouds TMC-1 and L134N, and the expanding circumstellar envelope IRC +10216. Our review has led to the proposal of new values and uncertainties for the rate coefficients of many of the key reactions. The impact of these new data on the predicted abundances in TMC-1 and L134N is reported. Interstellar dust p...

  15. Uncertainty quantification for quantum chemical models of complex reaction networks.

    Proppe, Jonny; Husch, Tamara; Simm, Gregor N; Reiher, Markus


    For the quantitative understanding of complex chemical reaction mechanisms, it is, in general, necessary to accurately determine the corresponding free energy surface and to solve the resulting continuous-time reaction rate equations for a continuous state space. For a general (complex) reaction network, it is computationally hard to fulfill these two requirements. However, it is possible to approximately address these challenges in a physically consistent way. On the one hand, it may be sufficient to consider approximate free energies if a reliable uncertainty measure can be provided. On the other hand, a highly resolved time evolution may not be necessary to still determine quantitative fluxes in a reaction network if one is interested in specific time scales. In this paper, we present discrete-time kinetic simulations in discrete state space taking free energy uncertainties into account. The method builds upon thermo-chemical data obtained from electronic structure calculations in a condensed-phase model. Our kinetic approach supports the analysis of general reaction networks spanning multiple time scales, which is here demonstrated for the example of the formose reaction. An important application of our approach is the detection of regions in a reaction network which require further investigation, given the uncertainties introduced by both approximate electronic structure methods and kinetic models. Such cases can then be studied in greater detail with more sophisticated first-principles calculations and kinetic simulations.

  16. Modeling Corrosion Reactions of Steel in a Dilute Carbonate Solution

    Eliyan, Faysal Fayez; Alfantazi, Akram


    This research models the corrosion reactions of a high-strength steel in an aerated, dilute, carbonate solution during a single-cycle voltammetry. Based on a previous study (Eliyan et al. in J Mater Eng Perform 24(6):1-8, 2015) and a literature survey, the corrosion reactions of the cathodic reduction, anodic dissolution, and passivation, as well as the interfacial interactions and the chemistry of the corrosion products are illustrated in schematics. The paper provides a visual guide on the corrosion reactions for steel in carbonate solutions based on the available mechanistic details that were reported and are still being investigated in literature.

  17. Extracting the invariant model from the feedback paths of digital hearing aids

    Ma, Guilin; Gran, Fredrik; Jacobsen, Finn;


    Feedback whistling is a severe problem with hearing aids. A typical acoustical feedback path represents a wave propagation path from the receiver to the microphone and includes many complicated effects among which some are invariant or nearly invariant for all users and in all acoustical environm...

  18. The path integral representation kernel of evolution operator in Merton-Garman model

    Blazhyevskyi, L F; 10.5488/CMP.14.23001


    In the framework of path integral the evolution operator kernel for the Merton-Garman Hamiltonian is constructed. Based on this kernel option formula is obtained, which generalizes the well-known Black-Scholes result. Possible approximation numerical schemes for path integral calculations are proposed.

  19. Theoretical Model Calculation for d + 8Li Reaction

    HAN Yin-Lu; GUO Hai-Rui; ZHANG Yue; ZHANG Jing-Shang


    Based on the theoretical models for light nuclei, the calculations of reaction cross sections and the angular distributions for d+8Li reaction are performed. Since all of the particle emissions are from the compound nucleus to the discrete levels, the angular momentum coupling effect in pre-equilibrium mechanism is taken into account. The three-body break-up process and the recoil effect are involved. The theoretical calculated results are compared to existing experimental data.

  20. An Investigation of Model Catalyzed Hydrocarbon Formation Reactions

    Tysoe, W. T.


    Work was focused on two areas aimed at understanding the chemistry of realistic catalytic systems: (1) The synthesis and characterization of model supported olefin metathesis catalysts. (2) Understanding the role of the carbonaceous layer present on Pd(111) single crystal model catalysts during reaction.

  1. Model-order reduction of biochemical reaction networks

    Rao, Shodhan; Schaft, Arjan van der; Eunen, Karen van; Bakker, Barbara M.; Jayawardhana, Bayu


    In this paper we propose a model-order reduction method for chemical reaction networks governed by general enzyme kinetics, including the mass-action and Michaelis-Menten kinetics. The model-order reduction method is based on the Kron reduction of the weighted Laplacian matrix which describes the gr

  2. Statistical mechanics and field theory. [Path integrals, lattices, pseudofree vertex model

    Samuel, S.A.


    Field theory methods are applied to statistical mechanics. Statistical systems are related to fermionic-like field theories through a path integral representation. Considered are the Ising model, the free-fermion model, and close-packed dimer problems on various lattices. Graphical calculational techniques are developed. They are powerful and yield a simple procedure to compute the vacuum expectation value of an arbitrary product of Ising spin variables. From a field theorist's point of view, this is the simplest most logical derivation of the Ising model partition function and correlation functions. This work promises to open a new area of physics research when the methods are used to approximate unsolved problems. By the above methods a new model named the 128 pseudo-free vertex model is solved. Statistical mechanics intuition is applied to field theories. It is shown that certain relativistic field theories are equivalent to classical interacting gases. Using this analogy many results are obtained, particularly for the Sine-Gordon field theory. Quark confinement is considered. Although not a proof of confinement, a logical, esthetic, and simple picture is presented of how confinement works. A key ingredient is the insight gained by using an analog statistical system consisting of a gas of macromolecules. This analogy allows the computation of Wilson loops in the presence of topological vortices and when symmetry breakdown occurs in the topological quantum number. Topological symmetry breakdown calculations are placed on approximately the same level of rigor as instanton calculations. The picture of confinement that emerges is similar to the dual Meissner type advocated by Mandelstam. Before topological symmetry breakdown, QCD has monopoles bound linearly together by three topological strings. Topological symmetry breakdown corresponds to a new phase where these monopoles are liberated. It is these liberated monopoles that confine quarks. 64 references.

  3. The fundamental Diagram of Pedestrian Model with Slow Reaction

    Fang, Jun; Hu, Hao; Xu, Zhaohui; Li, Huan


    The slow-to-start models are a classical cellular automata model in simulating vehicle traffic. However, to our knowledge, the slow-to-start effect has not considered in modeling pedestrian dynamic. We verify the similar behavior between pedestrian and vehicle, and propose an new lattice gas (LG) model called the slow reaction (SR) model to describe the pedestrian's delayed reaction in single-file movement. We simulate and reproduce the Seyfried's field experiments at the research centre Julich, and use its empirical data to validate our SR model. We compare the SR model with the standard LG model. We test different probability of slow reaction ps in SR model and found the simulation data of ps=0.3 fit the empirical data best. The RMS error of mean velocity of SR model is smaller than that of standard LG model. In the range of ps=0.1~0.3, our fundamental diagram between velocity and density by simulation coincides with field experiments. The distribution of individual velocity in fundamental diagram in SR mod...

  4. Water vapour permeability of poly(lactic acid): Crystallinity and the tortuous path model

    Duan, Z.; Thomas, N. L.


    The water vapour transmission rates (WVTR) through samples of polylactic acid of different crystallinities have been measured. Three different grades of commercial poly(lactic acid) (PLA) were used with different ratios of L-lactide and D-lactide to give a range of crystallinities from 0% to 50%. Sheets of PLA were prepared by melt compounding followed by compression moulding and annealing at different temperatures and for different times to give the range of crystallinities required. Crystallinity was measured by differential scanning calorimetry and the morphology of the samples was observed under crossed polars in a transmitted light microscope. Water vapour transmission rates through the films were measured at 38 °C and at a relative humidity of 90%. It was found that the measured values of WVTR decreased linearly with increasing crystallinity of the PLA from 0% to 50%. The results are discussed in terms of the effect of crystallinity on solubility and shown to fit the "Tortuous Path Model." The model was also successfully used to explain published data on water permeability of polyethylene terephthalate.




    Full Text Available The general path model (GPM is one approach for performing degradation-based, or Type III, prognostics. The GPM fits a parametric function to the collected observations of a prognostic parameter and extrapolates the fit to a failure threshold. This approach has been successfully applied to a variety of systems when a sufficient number of prognostic parameter observations are available. However, the parametric fit can suffer significantly when few data are available or the data are very noisy. In these instances, it is beneficial to include additional information to influence the fit to conform to a prior belief about the evolution of system degradation. Bayesian statistical approaches have been proposed to include prior information in the form of distributions of expected model parameters. This requires a number of run-to-failure cases with tracked prognostic parameters; these data may not be readily available for many systems. Reliability information and stressor-based (Type I and Type II, respectively prognostic estimates can provide the necessary prior belief for the GPM. This article presents the Bayesian updating framework to include prior information in the GPM and compares the efficacy of including different information sources on two data sets.

  6. Numerical modeling of 3D halo current path in ITER structures

    Bettini, Paolo; Marconato, Nicolò; Furno Palumbo, Maurizio; Peruzzo, Simone [Consorzio RFX, EURATOM-ENEA Association, Stati Uniti 4, 35127 Padova (Italy); Specogna, Ruben, E-mail: [DIEGM, Università di Udine, Via delle Scienze, 208, 33100 Udine (Italy); Albanese, Raffaele; Rubinacci, Guglielmo; Ventre, Salvatore; Villone, Fabio [Consorzio CREATE, EURATOM-ENEA Association, Via Claudio 21, 80125 Napoli (Italy)


    Highlights: ► Two numerical codes for the evaluation of halo currents in 3D structures are presented. ► A simplified plasma model is adopted to provide the input (halo current injected into the FW). ► Two representative test cases of ITER symmetric and asymmetric VDEs have been analyzed. ► The proposed approaches provide results in excellent agreement for both cases. -- Abstract: Disruptions represent one of the main concerns for Tokamak operation, especially in view of fusion reactors, or experimental test reactors, due to the electro-mechanical loads induced by halo and eddy currents. The development of a predictive tool which allows to estimate the magnitude and spatial distribution of the halo current forces is of paramount importance in order to ensure robust vessel and in-vessel component design. With this aim, two numerical codes (CARIDDI, CAFE) have been developed, which allow to calculate the halo current path (resistive distribution) in the passive structures surrounding the plasma. The former is based on an integral formulation for the eddy currents problem particularized to the static case; the latter implements a pair of 3D FEM complementary formulations for the solution of the steady-state current conduction problem. A simplified plasma model is adopted to provide the inputs (halo current injected into the first wall). Two representative test cases (ITER symmetric and asymmetric VDEs) have been selected to cross check the results of the proposed approaches.

  7. Oscillation Susceptibility Analysis of the ADMIRE Aircraft along the Path of Longitudinal Flight Equilibriums in Two Different Mathematical Models

    Achim Ionita


    Full Text Available The oscillation susceptibility of the ADMIRE aircraft along the path of longitudinal flight equilibriums is analyzed numerically in the general and in a simplified flight model. More precisely, the longitudinal flight equilibriums, the stability of these equilibriums, and the existence of bifurcations along the path of these equilibriums are researched in both models. Maneuvers and appropriate piloting tasks for the touch-down moment are simulated in both models. The computed results obtained in the models are compared in order to see if the movement concerning the landing phase computed in the simplified model is similar to that computed in the general model. The similarity we find is not a proof of the structural stability of the simplified system, what as far we know never been made, but can increase the confidence that the simplified system correctly describes the real phenomenon.

  8. A simple model for the estimation of rain-induced attenuation along earth-space paths at millimeter wavelengths

    Stutzman, W. L.; Dishman, W. K.


    A simple attenuation model (SAM) is presented for estimating rain-induced attenuation along an earth-space path. The rain model uses an effective spatial rain distribution which is uniform for low rain rates and which has an exponentially shaped horizontal rain profile for high rain rates. When compared to other models, the SAM performed well in the important region of low percentages of time, and had the lowest percent standard deviation of all percent time values tested.

  9. Path Loss, Shadow Fading, and Line-Of-Sight Probability Models for 5G Urban Macro-Cellular Scenarios

    Sun, Shu; Thomas, Timothy; Rappaport, Theodore S.


    This paper presents key parameters including the line-of-sight (LOS) probability, large-scale path loss, and shadow fading models for the design of future fifth generation (5G) wireless communication systems in urban macro-cellular (UMa) scenarios, using the data obtained from propagation measure...

  10. Path Integrals and Hamiltonians

    Baaquie, Belal E.


    1. Synopsis; Part I. Fundamental Principles: 2. The mathematical structure of quantum mechanics; 3. Operators; 4. The Feynman path integral; 5. Hamiltonian mechanics; 6. Path integral quantization; Part II. Stochastic Processes: 7. Stochastic systems; Part III. Discrete Degrees of Freedom: 8. Ising model; 9. Ising model: magnetic field; 10. Fermions; Part IV. Quadratic Path Integrals: 11. Simple harmonic oscillators; 12. Gaussian path integrals; Part V. Action with Acceleration: 13. Acceleration Lagrangian; 14. Pseudo-Hermitian Euclidean Hamiltonian; 15. Non-Hermitian Hamiltonian: Jordan blocks; 16. The quartic potential: instantons; 17. Compact degrees of freedom; Index.

  11. Implementation of a vibrationally linked chemical reaction model for DSMC

    Carlson, A. B.; Bird, Graeme A.


    A new procedure closely linking dissociation and exchange reactions in air to the vibrational levels of the diatomic molecules has been implemented in both one- and two-dimensional versions of Direct Simulation Monte Carlo (DSMC) programs. The previous modeling of chemical reactions with DSMC was based on the continuum reaction rates for the various possible reactions. The new method is more closely related to the actual physics of dissociation and is more appropriate to the particle nature of DSMC. Two cases are presented: the relaxation to equilibrium of undissociated air initially at 10,000 K, and the axisymmetric calculation of shuttle forebody heating during reentry at 92.35 km and 7500 m/s. Although reaction rates are not used in determining the dissociations or exchange reactions, the new method produces rates which agree astonishingly well with the published rates derived from experiment. The results for gas properties and surface properties also agree well with the results produced by earlier DSMC models, equilibrium air calculations, and experiment.


    江成顺; 刘蕴贤; 沈永明


    This paper is concerned with some nonlinear reaction - diffusion models. To solve this kind of models, the modified Laplace finite element scheme and the alternating direction finite element scheme are established for the system of patrical differential equations. Besides, the finite difference method is utilized for the ordinary differential equation in the models. Moreover, by the theory and technique of prior estimates for the differential equations, the convergence analyses and the optimal L2- norm error estimates are demonstrated.

  13. Predicting the distribution of spiral waves from cell properties in a developmental-path model of Dictyostelium pattern formation.

    Daniel Geberth


    Full Text Available The slime mold Dictyostelium discoideum is one of the model systems of biological pattern formation. One of the most successful answers to the challenge of establishing a spiral wave pattern in a colony of homogeneously distributed D. discoideum cells has been the suggestion of a developmental path the cells follow (Lauzeral and coworkers. This is a well-defined change in properties each cell undergoes on a longer time scale than the typical dynamics of the cell. Here we show that this concept leads to an inhomogeneous and systematic spatial distribution of spiral waves, which can be predicted from the distribution of cells on the developmental path. We propose specific experiments for checking whether such systematics are also found in data and thus, indirectly, provide evidence of a developmental path.

  14. Quantum toy model for black-hole back-reaction

    Maia, Clovis


    We propose a simple quantum field theoretical toy model for black hole evaporation and study the back-reaction of Hawking radiation onto the classical background. It turns out that the horizon is also ``pushed back'' in this situation (i.e., the interior region shrinks) but this back-reaction is not caused by energy conservation but by momentum balance. The effective heat capacity and the induced entropy variation can have both signs -- depending on the parameters of the model. PACS: 04.62.+v, 04.70.Dy.

  15. Carbon sequestration via reaction with basaltic rocks: geochemical modeling and experimental results

    Rosenbauer, Robert J.; Thomas, Burt; Bischoff, James L.; Palandri, James


    Basaltic rocks are potential repositories for sequestering carbon dioxide (CO2) because of their capacity for trapping CO2 in carbonate minerals. We carried out a series of thermodynamic equilibrium models and high pressure experiments, reacting basalt with CO2-charged fluids over a range of conditions from 50 to 200 °C at 300 bar. Results indicate basalt has a high reactivity to CO2 acidified brine. Carbon dioxide is taken up from solution at all temperatures from 50 to 200 °C, 300 bar, but the maximum extent and rate of reaction occurs at 100 °C, 300 bar. Reaction path simulations utilizing the geochemical modeling program CHILLER predicted an equilibrium carbonate alteration assemblage of calcite, magnesite, and siderite, but the only secondary carbonate identified in the experiments was a ferroan magnesite. The amount of uptake at 100 °C, 300 bar ranged from 8% by weight for a typical tholeite to 26% for a picrite. The actual amount of CO2 uptake and extent of rock alteration coincides directly with the magnesium content of the rock suggesting that overall reaction extent is controlled by bulk basalt Mg content. In terms of sequestering CO2, an average basaltic MgO content of 8% is equivalent to 2.6 × 108 metric ton CO2/km3 basalt.

  16. The Coherence Formation Model of Illustrated Text Comprehension: A Path Model of Attention to Multimedia Text

    Fitzhugh, Shannon Leigh


    The study reported here tests a model that includes several factors thought to contribute to the comprehension of static multimedia learning materials (i.e. background knowledge, working memory, attention to components as measured with eye movement measures). The model examines the effects of working memory capacity, domain specific (biology) and…

  17. The Coherence Formation Model of Illustrated Text Comprehension: A Path Model of Attention to Multimedia Text

    Fitzhugh, Shannon Leigh


    The study reported here tests a model that includes several factors thought to contribute to the comprehension of static multimedia learning materials (i.e. background knowledge, working memory, attention to components as measured with eye movement measures). The model examines the effects of working memory capacity, domain specific (biology) and…

  18. Path integration and cognitive mapping in a continuous attractor neural network model.

    Samsonovich, A; McNaughton, B L


    A minimal synaptic architecture is proposed for how the brain might perform path integration by computing the next internal representation of self-location from the current representation and from the perceived velocity of motion. In the model, a place-cell assembly called a "chart" contains a two-dimensional attractor set called an "attractor map" that can be used to represent coordinates in any arbitrary environment, once associative binding has occurred between chart locations and sensory inputs. In hippocampus, there are different spatial relations among place fields in different environments and behavioral contexts. Thus, the same units may participate in many charts, and it is shown that the number of uncorrelated charts that can be encoded in the same recurrent network is potentially quite large. According to this theory, the firing of a given place cell is primarily a cooperative effect of the activity of its neighbors on the currently active chart. Therefore, it is not particularly useful to think of place cells as encoding any particular external object or event. Because of its recurrent connections, hippocampal field CA3 is proposed as a possible location for this "multichart" architecture; however, other implementations in anatomy would not invalidate the main concepts. The model is implemented numerically both as a network of integrate-and-fire units and as a "macroscopic" (with respect to the space of states) description of the system, based on a continuous approximation defined by a system of stochastic differential equations. It provides an explanation for a number of hitherto perplexing observations on hippocampal place fields, including doubling, vanishing, reshaping in distorted environments, acquiring directionality in a two-goal shuttling task, rapid formation in a novel environment, and slow rotation after disorientation. The model makes several new predictions about the expected properties of hippocampal place cells and other cells of the

  19. Mathematical analysis study for radar data processing and enchancement. Part 2: Modeling of propagation path errors

    James, R.; Brownlow, J. D.


    A study is performed under NASA contract to evaluate data from an AN/FPS-16 radar installed for support of flight programs at Dryden Flight Research Facility of NASA Ames Research Center. The purpose of this study is to provide information necessary for improving post-flight data reduction and knowledge of accuracy of derived radar quantities. Tracking data from six flights are analyzed. Noise and bias errors in raw tracking data are determined for each of the flights. A discussion of an altitude bias error during all of the tracking missions is included. This bias error is defined by utilizing pressure altitude measurements made during survey flights. Four separate filtering methods, representative of the most widely used optimal estimation techniques for enhancement of radar tracking data, are analyzed for suitability in processing both real-time and post-mission data. Additional information regarding the radar and its measurements, including typical noise and bias errors in the range and angle measurements, is also presented. This report is in two parts. This is part 2, a discussion of the modeling of propagation path errors.

  20. Modelling population growth with delayed nonlocal reaction in 2-dimensions.

    Liang, Dong; Wu, Jianhong; Zhang, Fan


    In this paper, we consider the population growth of a single species living in a two-dimensional spatial domain. New reaction-difusion equation models with delayed nonlocal reaction are developed in two-dimensional bounded domains combining diferent boundary conditions. The important feature of the models is the reflection of the joint efect of the difusion dynamics and the nonlocal maturation delayed efect. We consider and ana- lyze numerical solutions of the mature population dynamics with some wellknown birth functions. In particular, we observe and study the occurrences of asymptotically stable steady state solutions and periodic waves for the two-dimensional problems with nonlocal delayed reaction. We also investigate numerically the efects of various parameters on the period, the peak and the shape of the periodic wave as well as the shape of the asymptotically stable steady state solution.

  1. An Empirical Outdoor-to-Indoor Path Loss Model from below 6 GHz to cm-Wave Frequency Bands

    Rodriguez Larrad, Ignacio; Nguyen, Huan Cong; Kovács, István Z.;


    This letter presents an empirical multi-frequency outdoor-to-indoor path loss model. The model is based on measurements performed on the exact same set of scenarios for different frequency bands ranging from traditional cellular allocations below 6 GHz (0.8, 2, 3.5 and 5.2 GHz), up to cm-wave fre......This letter presents an empirical multi-frequency outdoor-to-indoor path loss model. The model is based on measurements performed on the exact same set of scenarios for different frequency bands ranging from traditional cellular allocations below 6 GHz (0.8, 2, 3.5 and 5.2 GHz), up to cm...

  2. Elastodynamic modeling and joint reaction prediction for 3-PRS PKM

    张俊; 赵艳芹


    To gain a thorough understanding of the load state of parallel kinematic machines (PKMs), a methodology of elastodynamic modeling and joint reaction prediction is proposed. For this purpose, a Sprint Z3 model is used as a case study to illustrate the process of joint reaction analysis. The substructure synthesis method is applied to deriving an analytical elastodynamic model for the 3-PRS PKM device, in which the compliances of limbs and joints are considered. Each limb assembly is modeled as a spatial beam with non-uniform cross-section supported by lumped virtual springs at the centers of revolute and spherical joints. By introducing the deformation compatibility conditions between the limbs and the platform, the governing equations of motion of the system are obtained. After degenerating the governing equations into quasi-static equations, the effects of the gravity on system deflections and joint reactions are investigated with the purpose of providing useful information for the kinematic calibration and component strength calculations as well as structural optimizations of the 3-PRS PKM module. The simulation results indicate that the elastic deformation of the moving platform in the direction of gravity caused by gravity is quite large and cannot be ignored. Meanwhile, the distributions of joint reactions are axisymmetric and position-dependent. It is worthy to note that the proposed elastodynamic modeling method combines the benefits of accuracy of finite element method and concision of analytical method so that it can be used to predict the stiffness characteristics and joint reactions of a PKM throughout its entire workspace in a quick and accurate manner. Moreover, the present model can also be easily applied to evaluating the overall rigidity performance as well as statics of other PKMs with high efficiency after minor modifications.

  3. A Multiple Reaction Modelling Framework for Microbial Electrochemical Technologies

    Oyetunde, Tolutola; Sarma, Priyangshu M.; Ahmad, Farrukh; Rodríguez, Jorge


    A mathematical model for the theoretical evaluation of microbial electrochemical technologies (METs) is presented that incorporates a detailed physico-chemical framework, includes multiple reactions (both at the electrodes and in the bulk phase) and involves a variety of microbial functional groups. The model is applied to two theoretical case studies: (i) A microbial electrolysis cell (MEC) for continuous anodic volatile fatty acids (VFA) oxidation and cathodic VFA reduction to alcohols, for which the theoretical system response to changes in applied voltage and VFA feed ratio (anode-to-cathode) as well as membrane type are investigated. This case involves multiple parallel electrode reactions in both anode and cathode compartments; (ii) A microbial fuel cell (MFC) for cathodic perchlorate reduction, in which the theoretical impact of feed flow rates and concentrations on the overall system performance are investigated. This case involves multiple electrode reactions in series in the cathode compartment. The model structure captures interactions between important system variables based on first principles and provides a platform for the dynamic description of METs involving electrode reactions both in parallel and in series and in both MFC and MEC configurations. Such a theoretical modelling approach, largely based on first principles, appears promising in the development and testing of MET control and optimization strategies. PMID:28054959

  4. Neutrino nucleus reactions within the GiBUU model

    Lalakulich, O; Mosel, U


    The GiBUU model, which implements all reaction channels relevant at medium neutrino energy, is used to investigate the neutrino and antineutrino scattering on iron. Results for integrated cross sections are compared with NOMAD and MINOS data. It is shown, that final state interaction can noticeably change the spectra of the outgoing hadrons. Predictions for the Miner$\

  5. Modeling of calcium-based sorbent reactions with sulfur dioxide

    Tomanović Ivan


    Full Text Available A mathematical model of calcium sorbent reactions for simulation of sulfur dioxide reduction from pulverized coal combustion fl e gasses is developed, implemented within numerical code and validated against available measurements under controlled conditions. The model attempts to closely resemble reactions of calcination, sintering and sulfation, occurring during the sorbent particles motion in the furnace. The sulfation is based on PSSM (Partially Sintered Spheres Model, coupled with simulated particle calcination and sintering. Complex geometry of the particle is taken into account, with the assumption that it consists of spherical grains in contact with each other. Numerical simulations of drop down tube reactors were performed for both CaCO3 and Ca(OH2 sorbent particles and results were compared with available experimental data from literature. The sorbent reactions model will be further used for simulations of desulfurization reactions in turbulent gas-particle flow under coalcombustion conditions. [Projekat Ministarstva nauke Republike Srbije, br. TR-33018: Increase in energy and ecology efficiency of processes in pulverized coal-fired furnace and optimization of utility steam boiler air preheater by using in-house developed software tools

  6. Python framework for kinetic modeling of electronically excited reaction pathways

    Verboncoeur, John; Parsey, Guy; Guclu, Yaman; Christlieb, Andrew


    The use of plasma energy to enhance and control the chemical reactions during combustion, a technology referred to as ``plasma assisted combustion'' (PAC), can result in a variety of beneficial effects: e.g. stable lean operation, pollution reduction, and wider range of p-T operating conditions. While experimental evidence abounds, theoretical understanding of PAC is at best incomplete, and numerical tools still lack in reliable predictive capabilities. In the context of a joint experimental-numerical effort at Michigan State University, we present here an open-source modular Python framework dedicated to the dynamic optimization of non-equilibrium PAC systems. Multiple sources of experimental reaction data, e.g. reaction rates, cross-sections and oscillator strengths, are used in order to quantify the effect of data uncertainty and limiting assumptions. A collisional-radiative model (CRM) is implemented to organize reactions by importance and as a potential means of measuring a non-Maxwellian electron energy distribution function (EEDF), when coupled to optical emission spectroscopy data. Finally, we explore scaling laws in PAC parameter space using a kinetic global model (KGM) accelerated with CRM optimized reaction sequences and sparse stiff integrators.

  7. Cohabitation reaction-diffusion model for virus focal infections

    Amor, Daniel R.; Fort, Joaquim


    The propagation of virus infection fronts has been typically modeled using a set of classical (noncohabitation) reaction-diffusion equations for interacting species. However, for some single-species systems it has been recently shown that noncohabitation reaction-diffusion equations may lead to unrealistic descriptions. We argue that previous virus infection models also have this limitation, because they assume that a virion can simultaneously reproduce inside a cell and diffuse away from it. For this reason, we build a several-species cohabitation model that does not have this limitation. Furthermore, we perform a sensitivity analysis for the most relevant parameters of the model, and we compare the predicted infection speed with observed data for two different strains of the T7 virus.

  8. Modeling violent reaction following low speed impact on confined explosives

    Curtis, John Philip; Jones, Andrew; Hughes, Christopher; Reaugh, John


    To ensure the safe storage and deployment of explosives it is important to understand the mechanisms that give rise to ignition and reaction growth in low speed impacts. The High Explosive Response to Mechanical Stimulus (HERMES) material model, integrated in the Lagrangian code LSDYNA, has been developed to model the progress of the reaction after such an impact. The low speed impact characteristics of an HMX based formulation have been examined using the AWE Steven Test. Axisymmetric simulations of an HMX explosive in the AWE Steven Test have been performed. A sensitivity study included the influence of friction, mesh resolution, and confinement. By comparing the experimental and calculated results, key model parameters which determine the explosive's response in this configuration have been identified. The model qualitatively predicts the point of ignition within the vehicle. Future refinements are discussed.

  9. Complex reaction noise in a molecular quasispecies model

    Hochberg, David; Zorzano, María-Paz; Morán, Federico


    We have derived exact Langevin equations for a model of quasispecies dynamics. The inherent multiplicative reaction noise is complex and its statistical properties are specified completely. The numerical simulation of the complex Langevin equations is carried out using the Cholesky decomposition for the noise covariance matrix. This internal noise, which is due to diffusion-limited reactions, produces unavoidable spatio-temporal density fluctuations about the mean field value. In two dimensions, this noise strictly vanishes only in the perfectly mixed limit, a situation difficult to attain in practice.

  10. A path model of the relationship between career indecision, androgyny, self-efficacy, and self-esteem.

    Wulff, M B; Steitz, J A


    Utilizing a path model, this study investigated the relationship between Androgyny and career decision-making among 91 high school girls. The constructs included in the model were Androgyny as assessed by the Bem Sex-role Inventory, Self-esteem as assessed by the Rosenberg Self-esteem Scale, Self-efficacy as assessed by the Wulff-Steitz Career Self-efficacy Scale, and Career Indecision as assessed by the Osipow Career Decision Scale. The results indicated that Androgyny scores were significantly associated with those on Self-esteem, Self-esteem with Self-efficacy, and Self-efficacy with Career Indecision. The results are discussed in terms of the usefulness of path models in clarifying complex interrelationships.

  11. Tailoring a non-path-dependent model for environmental risk management and polycentric urban land-use planning.

    Sakieh, Yousef; Salmanmahiny, Abdolrassoul; Mirkarimi, Seyed Hamed


    This study attempts to develop a non-path-dependent model for environmental risk management and polycentric urban land-use planning in Gorgan Township area, Iran. Applying three suitability layers of environmental risk (soil erosion, flood risk, fire risk, and land susceptibility), urbanization potential, and integrated surface (environmental risk plus urbanization potential layers), a non-path-dependent Cellular Automata-Markov Chain (CA-MC) model was configured to execute three scenarios of polycentric urban growth allocation. Specifically, the modeling approach improved the traditional functionality of the CA-MC model from a prediction algorithm into an innovative land allocation tool. Besides, due to its flexibility, the non-path-dependent model was able to explicitly include different characteristics of the landscape structure ranging from physical land attributes to landscape functions and processes (natural hazards). Accordingly, three polycentric urban growth allocation efforts were undertaken and compared in terms of connectivity and compactness of the resultant patterns and consumption of other land resources. Based on results, the polycentric allocation procedure based on integrated suitability layer produced a more manageable pattern of urban landscape, while the growth option based on environmental risk layer was more successful for protecting farmlands against excessive urbanization. This study suggests that polycentric urban land-use planning under the strategy of rural land development programs is an available option for designing an urban landscape with lower exposure to natural hazards and more economic benefits to rural residents. Finally, the non-path-dependent modeling is a recommended approach, when highly flexible and interactive decision-support systems as well as trend-breaking scenarios are desired.

  12. Impact of Nuclear Reaction Uncertainties on AGB Nucleosynthesis Models

    Bisterzo, S; Kaeppeler, F; Wiescher, M; Travaglio, C


    Asymptotic giant branch (AGB) stars with low initial mass (1 - 3 Msun) are responsible for the production of neutron-capture elements through the main s-process (main slow neutron capture process). The major neutron source is 13C(alpha, n)16O, which burns radiatively during the interpulse periods at about 8 keV and produces a rather low neutron density (10^7 n/cm^3). The second neutron source 22Ne(alpha, n)25Mg, partially activated during the convective thermal pulses when the energy reaches about 23 keV, gives rise to a small neutron exposure but a peaked neutron density (Nn(peak) > 10^11 n/cm^3). At metallicities close to solar, it does not substantially change the final s-process abundances, but mainly affects the isotopic ratios near s-path branchings sensitive to the neutron density. We examine the effect of the present uncertainties of the two neutron sources operating in AGB stars, as well as the competition with the 22Ne(alpha, gamma)26Mg reaction. The analysis is carried out on AGB the main-s process...

  13. BlenX-based compositional modeling of complex reaction mechanisms

    Zámborszky, Judit; 10.4204/EPTCS.19.6


    Molecular interactions are wired in a fascinating way resulting in complex behavior of biological systems. Theoretical modeling provides a useful framework for understanding the dynamics and the function of such networks. The complexity of the biological networks calls for conceptual tools that manage the combinatorial explosion of the set of possible interactions. A suitable conceptual tool to attack complexity is compositionality, already successfully used in the process algebra field to model computer systems. We rely on the BlenX programming language, originated by the beta-binders process calculus, to specify and simulate high-level descriptions of biological circuits. The Gillespie's stochastic framework of BlenX requires the decomposition of phenomenological functions into basic elementary reactions. Systematic unpacking of complex reaction mechanisms into BlenX templates is shown in this study. The estimation/derivation of missing parameters and the challenges emerging from compositional model buildin...

  14. Modeling the effects of Multi-path propagation and scintillation on GPS signals

    Habash Krause, L.; Wilson, S. J.


    GPS signals traveling through the earth's ionosphere are affected by charged particles that often disrupt the signal and the information it carries due to "scintillation", which resembles an extra noise source on the signal. These signals are also affected by weather changes, tropospheric scattering, and absorption from objects due to multi-path propagation of the signal. These obstacles cause distortion within information and fading of the signal, which ultimately results in phase locking errors and noise in messages. In this work, we attempted to replicate the distortion that occurs in GPS signals using a signal processing simulation model. We wanted to be able to create and identify scintillated signals so we could better understand the environment that caused it to become scintillated. Then, under controlled conditions, we simulated the receiver's ability to suppress scintillation in a signal. We developed a code in MATLAB that was programmed to: 1. Create a carrier wave and then plant noise (four different frequencies) on the carrier wave, 2. Compute a Fourier transform on the four different frequencies to find the frequency content of a signal, 3. Use a filter and apply it to the Fourier transform of the four frequencies and then compute a Signal-to-noise ratio to evaluate the power (in Decibels) of the filtered signal, and 4.Plot each of these components into graphs. To test the code's validity, we used user input and data from an AM transmitter. We determined that the amplitude modulated signal or AM signal would be the best type of signal to test the accuracy of the MATLAB code due to its simplicity. This code is basic to give students the ability to change and use it to determine the environment and effects of noise on different AM signals and their carrier waves. Overall, we were able to manipulate a scenario of a noisy signal and interpret its behavior and change due to its noisy components: amplitude, frequency, and phase shift.

  15. Modelling biochemical reaction systems by stochastic differential equations with reflection.

    Niu, Yuanling; Burrage, Kevin; Chen, Luonan


    In this paper, we gave a new framework for modelling and simulating biochemical reaction systems by stochastic differential equations with reflection not in a heuristic way but in a mathematical way. The model is computationally efficient compared with the discrete-state Markov chain approach, and it ensures that both analytic and numerical solutions remain in a biologically plausible region. Specifically, our model mathematically ensures that species numbers lie in the domain D, which is a physical constraint for biochemical reactions, in contrast to the previous models. The domain D is actually obtained according to the structure of the corresponding chemical Langevin equations, i.e., the boundary is inherent in the biochemical reaction system. A variant of projection method was employed to solve the reflected stochastic differential equation model, and it includes three simple steps, i.e., Euler-Maruyama method was applied to the equations first, and then check whether or not the point lies within the domain D, and if not perform an orthogonal projection. It is found that the projection onto the closure D¯ is the solution to a convex quadratic programming problem. Thus, existing methods for the convex quadratic programming problem can be employed for the orthogonal projection map. Numerical tests on several important problems in biological systems confirmed the efficiency and accuracy of this approach.

  16. Modeling the Liquid Water Transport in the Gas Diffusion Layer for Polymer Electrolyte Membrane Fuel Cells Using a Water Path Network

    Dietmar Gerteisen; Robert Alink


    In order to model the liquid water transport in the porous materials used in polymer electrolyte membrane (PEM) fuel cells, the pore network models are often applied. The presented model is a novel approach to further develop these models towards a percolation model that is based on the fiber structure rather than the pore structure. The developed algorithm determines the stable liquid water paths in the gas diffusion layer (GDL) structure and the transitions from the paths to the subsequent ...

  17. EMPIRE: Nuclear Reaction Model Code System for Data Evaluation

    Herman, M.; Capote, R.; Carlson, B. V.; Obložinský, P.; Sin, M.; Trkov, A.; Wienke, H.; Zerkin, V.


    EMPIRE is a modular system of nuclear reaction codes, comprising various nuclear models, and designed for calculations over a broad range of energies and incident particles. A projectile can be a neutron, proton, any ion (including heavy-ions) or a photon. The energy range extends from the beginning of the unresolved resonance region for neutron-induced reactions (∽ keV) and goes up to several hundred MeV for heavy-ion induced reactions. The code accounts for the major nuclear reaction mechanisms, including direct, pre-equilibrium and compound nucleus ones. Direct reactions are described by a generalized optical model (ECIS03) or by the simplified coupled-channels approach (CCFUS). The pre-equilibrium mechanism can be treated by a deformation dependent multi-step direct (ORION + TRISTAN) model, by a NVWY multi-step compound one or by either a pre-equilibrium exciton model with cluster emission (PCROSS) or by another with full angular momentum coupling (DEGAS). Finally, the compound nucleus decay is described by the full featured Hauser-Feshbach model with γ-cascade and width-fluctuations. Advanced treatment of the fission channel takes into account transmission through a multiple-humped fission barrier with absorption in the wells. The fission probability is derived in the WKB approximation within the optical model of fission. Several options for nuclear level densities include the EMPIRE-specific approach, which accounts for the effects of the dynamic deformation of a fast rotating nucleus, the classical Gilbert-Cameron approach and pre-calculated tables obtained with a microscopic model based on HFB single-particle level schemes with collective enhancement. A comprehensive library of input parameters covers nuclear masses, optical model parameters, ground state deformations, discrete levels and decay schemes, level densities, fission barriers, moments of inertia and γ-ray strength functions. The results can be converted into ENDF-6 formatted files using the

  18. A model for reaction-assisted polymer dissolution in LIGA.

    Larson, Richard S.


    A new chemically-oriented mathematical model for the development step of the LIGA process is presented. The key assumption is that the developer can react with the polymeric resist material in order to increase the solubility of the latter, thereby partially overcoming the need to reduce the polymer size. The ease with which this reaction takes place is assumed to be determined by the number of side chain scissions that occur during the x-ray exposure phase of the process. The dynamics of the dissolution process are simulated by solving the reaction-diffusion equations for this three-component, two-phase system, the three species being the unreacted and reacted polymers and the solvent. The mass fluxes are described by the multicomponent diffusion (Stefan-Maxwell) equations, and the chemical potentials are assumed to be given by the Flory-Huggins theory. Sample calculations are used to determine the dependence of the dissolution rate on key system parameters such as the reaction rate constant, polymer size, solid-phase diffusivity, and Flory-Huggins interaction parameters. A simple photochemistry model is used to relate the reaction rate constant and the polymer size to the absorbed x-ray dose. The resulting formula for the dissolution rate as a function of dose and temperature is ?t to an extensive experimental data base in order to evaluate a set of unknown global parameters. The results suggest that reaction-assisted dissolution is very important at low doses and low temperatures, the solubility of the unreacted polymer being too small for it to be dissolved at an appreciable rate. However, at high doses or at higher temperatures, the solubility is such that the reaction is no longer needed, and dissolution can take place via the conventional route. These results provide an explanation for the observed dependences of both the dissolution rate and its activation energy on the absorbed dose.

  19. Developmental dysplasia of the hip: A computational biomechanical model of the path of least energy for closed reduction.

    Zwawi, Mohammed A; Moslehy, Faissal A; Rose, Christopher; Huayamave, Victor; Kassab, Alain J; Divo, Eduardo; Jones, Brendan J; Price, Charles T


    This study utilized a computational biomechanical model and applied the least energy path principle to investigate two pathways for closed reduction of high grade infantile hip dislocation. The principle of least energy when applied to moving the femoral head from an initial to a final position considers all possible paths that connect them and identifies the path of least resistance. Clinical reports of severe hip dysplasia have concluded that reduction of the femoral head into the acetabulum may occur by a direct pathway over the posterior rim of the acetabulum when using the Pavlik harness, or by an indirect pathway with reduction through the acetabular notch when using the modified Hoffman-Daimler method. This computational study also compared the energy requirements for both pathways. The anatomical and muscular aspects of the model were derived using a combination of MRI and OpenSim data. Results of this study indicate that the path of least energy closely approximates the indirect pathway of the modified Hoffman-Daimler method. The direct pathway over the posterior rim of the acetabulum required more energy for reduction. This biomechanical analysis confirms the clinical observations of the two pathways for closed reduction of severe hip dysplasia. The path of least energy closely approximated the modified Hoffman-Daimler method. Further study of the modified Hoffman-Daimler method for reduction of severe hip dysplasia may be warranted based on this computational biomechanical analysis. © 2016 The Authors. Journal of Orthopaedic Research Published by Wiley Periodicals, Inc. on behalf of Orthopaedic Research Society. J Orthop Res 35:1799-1805, 2017. © 2016 The Authors. Journal of Orthopaedic Research Published by Wiley Periodicals, Inc. on behalf of Orthopaedic Research Society.

  20. A model study of sequential enzyme reactions and electrostatic channeling.

    Eun, Changsun; Kekenes-Huskey, Peter M; Metzger, Vincent T; McCammon, J Andrew


    We study models of two sequential enzyme-catalyzed reactions as a basic functional building block for coupled biochemical networks. We investigate the influence of enzyme distributions and long-range molecular interactions on reaction kinetics, which have been exploited in biological systems to maximize metabolic efficiency and signaling effects. Specifically, we examine how the maximal rate of product generation in a series of sequential reactions is dependent on the enzyme distribution and the electrostatic composition of its participant enzymes and substrates. We find that close proximity between enzymes does not guarantee optimal reaction rates, as the benefit of decreasing enzyme separation is countered by the volume excluded by adjacent enzymes. We further quantify the extent to which the electrostatic potential increases the efficiency of transferring substrate between enzymes, which supports the existence of electrostatic channeling in nature. Here, a major finding is that the role of attractive electrostatic interactions in confining intermediate substrates in the vicinity of the enzymes can contribute more to net reactive throughput than the directional properties of the electrostatic fields. These findings shed light on the interplay of long-range interactions and enzyme distributions in coupled enzyme-catalyzed reactions, and their influence on signaling in biological systems.


    AbdulMunem A. Karim


    Full Text Available    This study deals with  kinetics of hydrodesulphurization (HDS reaction of vacuum gas oil (611-833 K which was distillated from Kirkuk crude oil and which was obtained by blending the fractions, light vacuum gas oil (611 - 650 K, medium vacuum gas oil (650-690 K, heavy vacuum gas oil (690-727 K and very heavy vacuum gas oil (727-833 K.   The vacuum gas oil was hydrotreated on a commercial cobalt-molybdenum alumina catalyst presulfied at specified conditions in a laboratory trickle bed reactor. The reaction temperature range (583-643 K,liquid hourly space velocity range (1.5-3.75 h-1 and hydrogen pressure was kept constant at 3.5 MPa with hydrogen to oil ratio about 250 lt/lt.           The conversion results for desulphurization reaction appeared to obey the second order reaction. According to this model, the rate constants for desulphurization reaction were determined. Finally, the apparent activation energy (Ea, enthalpy of activation ( H* and entropy ( S* were calculated based on the values of rate constant (k2 and were equal 80.3792 KJ/mole, 75.2974 KJ/mole and 197.493 J/mole, respectively.

  2. Modelling of structural effects on chemical reactions in turbulent flows

    Gammelsaeter, H.R.


    Turbulence-chemistry interactions are analysed using algebraic moment closure for the chemical reaction term. The coupling between turbulence and chemical length and time scales generate a complex interaction process. This interaction process is called structural effects in this work. The structural effects are shown to take place on all scales between the largest scale of turbulence and the scales of the molecular motions. The set of equations describing turbulent correlations involved in turbulent reacting flows are derived. Interactions are shown schematically using interaction charts. Algebraic equations for the turbulent correlations in the reaction rate are given using the interaction charts to include the most significant couplings. In the frame of fundamental combustion physics, the structural effects appearing on the small scales of turbulence are proposed modelled using a discrete spectrum of turbulent scales. The well-known problem of averaging the Arrhenius law, the specific reaction rate, is proposed solved using a presumed single variable probability density function and a sub scale model for the reaction volume. Although some uncertainties are expected, the principles are addressed. Fast chemistry modelling is shown to be consistent in the frame of algebraic moment closure when the turbulence-chemistry interaction is accounted for in the turbulent diffusion. The modelling proposed in this thesis is compared with experimental data for an laboratory methane flame and advanced probability density function modelling. The results show promising features. Finally it is shown a comparison with full scale measurements for an industrial burner. All features of the burner are captured with the model. 41 refs., 33 figs.

  3. Silicate glass and mineral dissolution: calculated reaction paths and activation energies for hydrolysis of a q3 si by H3O+ using ab initio methods.

    Criscenti, Louise J; Kubicki, James D; Brantley, Susan L


    Molecular orbital energy minimizations were performed with the B3LYP/6-31G(d) method on a [((OH)3SiO)3SiOH-(H3O+).4(H2O)] cluster to follow the reaction path for hydrolysis of an Si-O-Si linkage via proton catalysis in a partially solvated system. The Q3 molecule was chosen (rather than Q2 or Q1) to estimate the maximum activation energy for a fully relaxed cluster representing the surface of an Al-depleted acid-etched alkali feldspar. Water molecules were included in the cluster to investigate the influence of explicit solvation on proton-transfer reactions and on the energy associated with hydroxylating the bridging oxygen atom (Obr). Single-point energy calculations were performed with the B3LYP/6-311+G(d,p) method. Proton transfer from the hydronium cation to an Obr requires sufficient energy to suggest that the Si-(OH)-Si species will occur only in trace quantities on a silica surface. Protonation of the Obr lengthens the Si-Obr bond and allows for the formation of a pentacoordinate Si intermediate ([5]Si). The energy required to form this species is the dominant component of the activation energy barrier to hydrolysis. After formation of the pentacoordinate intermediate, hydrolysis occurs via breaking the [5]Si-(OH)-Si linkage with a minimal activation energy barrier. A concerted mechanism involving stretching of the [5]Si-(OH) bond, proton transfer from the Si-(OH2)+ back to form H3O+, and a reversion of [5]Si to tetrahedral coordination was predicted. The activation energy for Q3Si hydrolysis calculated here was found to be less than that reported for Q3Si using a constrained cluster in the literature but significantly greater than the measured activation energies for the hydrolysis of Si-Obr bonds in silicate minerals. These results suggest that the rate-limiting step in silicate dissolution is not the hydrolysis of Q3Si-Obr bonds but rather the breakage of Q2 or Q1Si-Obr bonds.

  4. Spallation reactions. A successful interplay between modeling and applications

    David, J -C


    The spallation reactions are a type of nuclear reaction which occur in space by interaction of the cosmic rays with interstellar bodies. The first spallation reactions induced with an accelerator took place in 1947 at the Berkeley cyclotron (University of California) with 200 MeV deuterons and 400 MeV alpha beams. They highlighted the multiple emission of neutrons and charged particles and the production of a large number of residual nuclei far different from the target nuclei. The same year R. Serber describes the reaction in two steps: a first and fast one with high-energy particle emission leading to an excited remnant nucleus, and a second one, much slower, the de-excitation of the remnant. In 2010 IAEA organized a worskhop to present the results of the most widely used spallation codes within a benchmark of spallation models. If one of the goals was to understand the deficiencies, if any, in each code, one remarkable outcome points out the overall high-quality level of some models and so the great improv...

  5. Multidimensional model of apathy in older adults using partial least squares--path modeling.

    Raffard, Stéphane; Bortolon, Catherine; Burca, Marianna; Gely-Nargeot, Marie-Christine; Capdevielle, Delphine


    Apathy defined as a mental state characterized by a lack of goal-directed behavior is prevalent and associated with poor functioning in older adults. The main objective of this study was to identify factors contributing to the distinct dimensions of apathy (cognitive, emotional, and behavioral) in older adults without dementia. One hundred and fifty participants (mean age, 80.42) completed self-rated questionnaires assessing apathy, emotional distress, anticipatory pleasure, motivational systems, physical functioning, quality of life, and cognitive functioning. Data were analyzed using partial least squares variance-based structural equation modeling in order to examine factors contributing to the three different dimensions of apathy in our sample. Overall, the different facets of apathy were associated with cognitive functioning, anticipatory pleasure, sensitivity to reward, and physical functioning, but the contribution of these different factors to the three dimensions of apathy differed significantly. More specifically, the impact of anticipatory pleasure and physical functioning was stronger for the cognitive than for emotional apathy. Conversely, the impact of sensibility to reward, although small, was slightly stronger on emotional apathy. Regarding behavioral apathy, again we found similar latent variables except for the cognitive functioning whose impact was not statistically significant. Our results highlight the need to take into account various mechanisms involved in the different facets of apathy in older adults without dementia, including not only cognitive factors but also motivational variables and aspects related to physical disability. Clinical implications are discussed.

  6. Towards many-body based nuclear reaction modelling

    Hilaire, Stéphane; Goriely, Stéphane


    The increasing need for cross sections far from the valley of stability poses a challenge for nuclear reaction models. So far, predictions of cross sections have relied on more or less phenomenological approaches, depending on parameters adjusted to available experimental data or deduced from systematic expressions. While such predictions are expected to be reliable for nuclei not too far from the experimentally known regions, it is clearly preferable to use more fundamental approaches, based on sound physical principles, when dealing with very exotic nuclei. Thanks to the high computer power available today, all the ingredients required to model a nuclear reaction can now be (and have been) microscopically (or semi-microscopically) determined starting from the information provided by a nucleon-nucleon effective interaction. This concerns nuclear masses, optical model potential, nuclear level densities, photon strength functions, as well as fission barriers. All these nuclear model ingredients, traditionally given by phenomenological expressions, now have a microscopic counterpart implemented in the TALYS nuclear reaction code. We are thus now able to perform fully microscopic cross section calculations. The quality of these ingredients and the impact of using them instead of the usually adopted phenomenological parameters will be discussed. Perspectives for the coming years will be drawn on the improvements one can expect.

  7. Modeling for Formation of Conducting Path in Cu/SiO2/Pt Memory Devices: Based on Soft Breakdown Mechanism

    Luo, J. M.


    The forming process before resistive switching in Cu/ SiO2/Pt memory devices, corresponding to the formation of conducting path, can be regarded as the dielectric soft breakdown. Based on the analysis of breakdown mechanism, a dynamic model combining the transition of Cu ions with the space-charge effect has been proposed, and demonstrates that the forming voltage depends on the thickness of oxide, the sweep rate of voltage and temperature. The predictions of the model are consistent with the experiment data reported in the literature and it is believed that the transition of Cu ions across the oxide and the accumulation of Cu ions at the SiO2/Pt interface could be responsible for the conductive path formation in Cu/SiO2/Pt memory devices.

  8. The Use of Partial Least Squares Path Modeling in Investigating the Relationship between Leadership, Motivation and Rewarding

    Elif BULUT


    Full Text Available The aim of this study is to introduce the partial least squares path modeling which is a new approach to structural equation modeling, representing the joint point between path analysis and confirmatory factor analysis. The use of this method was tried to be explained by examining the relationship between leadership, motivation and rewarding. Self-designed questionnaire was used for data collection. A private hospital was taken as the sample of the study. The analysis results conclude that there are statistically significant relationship between leadership and motivation and leadership and rewarding, separately. Additionally, the results show that rewarding has a statistically significant effect on motivation. The study also shows that the concepts that led to the establishment of leadership have an important place in the relationship between leadership and motivation. The positive effect of the fair rewarding system on motivation is also located between the results obtained from this study.

  9. Microstructural path analysis of martensite burst

    Paulo Rangel Rios


    Full Text Available Modeling the martensite reaction requires reckoning with spatial aspects of the reaction. For that, we used formal kinetics, more specifically, the microstructural path method (MPM to analyze the microstructure observed in a burst. The microstructural path analysis revealed that the size of the spread cluster in extended space, characterized by the Vandermeer and Juul-Jensen's impingement compensated mean intercept length, λG, remained constant, independently of the parent austenite grain size. Moreover, current analysis introduced a purely formal description of the reaction progress by taking the parent austenite grain size as the progress variable. This description worked very well and resulted in a relationship between the volume fraction of partially transformed austenite, V VG, and austenite grain size, λG. The significance of these findings in the light of the advantages and disadvantages of formal kinetics is discussed.

  10. Multiscale enhanced path sampling based on the Onsager-Machlup action: Application to a model polymer

    Fujisaki, Hiroshi; Moritsugu, Kei; Kidera, Akinori


    We propose a novel path sampling method based on the Onsager-Machlup (OM) action by generalizing the multiscale enhanced sampling (MSES) technique suggested by Moritsugu and coworkers (J. Chem. Phys. 133, 224105 (2010)). The basic idea of this method is that the system we want to study (for example, some molecular system described by molecular mechanics) is coupled to a coarse-grained (CG) system, which can move more quickly and computed more efficiently than the original system. We simulate this combined system (original + CG system) using (underdamped) Langevin dynamics where different heat baths are coupled to the two systems. When the coupling is strong enough, the original system is guided by the CG system, and able to sample the configuration and path space more efficiency. We need to correct the bias caused by the coupling, however, by employing the Hamiltonian replica exchange where we prepare many path replica with different coupling strengths. As a result, an unbiased path ensemble for the original ...

  11. A Path Model of Expressive Vocabulary Skills in Initially Preverbal Preschool Children with Autism Spectrum Disorder

    McDaniel, Jena; Yoder, Paul; Watson, Linda R.


    We examined direct and indirect paths involving receptive vocabulary and diversity of key consonants used in communication (DKCC) to improve understanding of why previously identified value-added predictors are associated with later expressive vocabulary for initially preverbal children with autism spectrum disorder (ASD; n = 87). Intentional…

  12. Microstructural path model and strain dependence of recrystallisation in commercial aluminium

    Vandermeer, Roy Allen; Wu, Guilin; Juul Jensen, Dorte


    The isothermal recrystallisation of commercial purity aluminium alloy AA1200 cold deformed to either a true strain of 2 (86.5% reduction in thickness) or 4 (98.2% reduction in thickness) was studied phenomenologically in each material by means of quantitative microscopy. The microstructural path ...

  13. Mathematical modeling of precipitation and dissolution reactions in microbiological systems.

    Rittmann, Bruce E; Banaszak, James E; VanBriesen, Jeanne M; Reed, Donald T


    We expand the biogeochemical model CCBATCH to include a precipitation/dissolution sub-model that contains kinetic and equilibrium options. This advancement extends CCBATCH's usefulness to situations in which microbial reactions cause or are affected by formation or dissolution of a solid phase. The kinetic option employs a rate expression that explicitly includes the intrinsic kinetics for reaction or mass-transport control, the difference from thermodynamic equilibrium, and the aqueous concentration of the rate-limiting metal or ligand. The equilibrium feature can be used alone, and it also serves as check that the kinetic rate never is too fast and "overshoots" equilibrium. The features of the expanded CCBATCH are illustrated by an example in which the precipitation of Fe(OH)3(s) allows the biodegradation of citric acid, even though complexes are strong and not bioavailable. Precipitation releases citrate ligand, and biodegradation of the citrate increases the pH.

  14. Closed Loop Adaptive Refinement of Dynamical Models for Complex Chemical Reactions


    CH3Br, Ar + H2O are given below. 3.1 Cl− + CH3Br Reaction A global RS-HDMR input/output map for the SN2 reaction Cl− +CH3Br→ ClCH3 +Br − (9) 3 was...2257-2266. [16] Wang H. B., Hase W. L. (1996). Reaction path Hamiltonian analysis of the dynamics for Cl− + CH3Br→ ClCH3 + Br − SN2 nucleophilic... reaction Cl − + CH3Br → ClCH3 + Br −, J. Chem. Phys., 111(24), 10887- 10894. [18] Sun, L., Hase, W. L., Song, K. (2001). Trajectory studies of SN2

  15. A unifying kinetic framework for modeling oxidoreductase-catalyzed reactions

    Chang, Ivan; Baldi, Pierre


    Motivation: Oxidoreductases are a fundamental class of enzymes responsible for the catalysis of oxidation–reduction reactions, crucial in most bioenergetic metabolic pathways. From their common root in the ancient prebiotic environment, oxidoreductases have evolved into diverse and elaborate protein structures with specific kinetic properties and mechanisms adapted to their individual functional roles and environmental conditions. While accurate kinetic modeling of oxidoreductases is thus imp...

  16. Kinetic modelling of GlmU reactions - prioritization of reaction for therapeutic application.

    Vivek K Singh

    Full Text Available Mycobacterium tuberculosis(Mtu, a successful pathogen, has developed resistance against the existing anti-tubercular drugs necessitating discovery of drugs with novel action. Enzymes involved in peptidoglycan biosynthesis are attractive targets for antibacterial drug discovery. The bifunctional enzyme mycobacterial GlmU (Glucosamine 1-phosphate N-acetyltransferase/ N-acetylglucosamine-1-phosphate uridyltransferase has been a target enzyme for drug discovery. Its C- and N- terminal domains catalyze acetyltransferase (rxn-1 and uridyltransferase (rxn-2 activities respectively and the final product is involved in peptidoglycan synthesis. However, the bifunctional nature of GlmU poses difficulty in deciding which function to be intervened for therapeutic advantage. Genetic analysis showed this as an essential gene but it is still unclear whether any one or both of the activities are critical for cell survival. Often enzymatic activity with suitable high-throughput assay is chosen for random screening, which may not be the appropriate biological function inhibited for maximal effect. Prediction of rate-limiting function by dynamic network analysis of reactions could be an option to identify the appropriate function. With a view to provide insights into biochemical assays with appropriate activity for inhibitor screening, kinetic modelling studies on GlmU were undertaken. Kinetic model of Mtu GlmU-catalyzed reactions was built based on the available kinetic data on Mtu and deduction from Escherichia coli data. Several model variants were constructed including coupled/decoupled, varying metabolite concentrations and presence/absence of product inhibitions. This study demonstrates that in coupled model at low metabolite concentrations, inhibition of either of the GlmU reactions cause significant decrement in the overall GlmU rate. However at higher metabolite concentrations, rxn-2 showed higher decrement. Moreover, with available intracellular

  17. Mathematical Model of Synthesis Catalyst with Local Reaction Centers

    I. V. Derevich


    Full Text Available The article considers a catalyst granule with a porous ceramic passive substrate and point active centers on which an exothermic synthesis reaction occurs. A rate of the chemical reaction depends on the temperature according to the Arrhenius law. Heat is removed from the pellet surface in products of synthesis due to heat transfer. In our work we first proposed a model for calculating the steady-state temperature of a catalyst pellet with local reaction centers. Calculation of active centers temperature is based on the idea of self-consistent field (mean-field theory. At first, it is considered that powers of the reaction heat release at the centers are known. On the basis of the found analytical solution, which describes temperature distribution inside the granule, the average temperature of the reaction centers is calculated, which then is inserted in the formula for heat release. The resulting system of transcendental algebraic equations is transformed into a system of ordinary differential equations of relaxation type and solved numerically to achieve a steady-state value. As a practical application, the article considers a Fischer-Tropsch synthesis catalyst granule with active cobalt metallic micro-particles. Cobalt micro-particles are the centers of the exothermic reaction of hydrocarbons macromolecular synthesis. Synthesis occurs as a result of absorption of the components of the synthesis gas on metallic cobalt. The temperature distribution inside the granule for a single local center and reaction centers located on the same granule diameter is found. It was found that there is a critical temperature of reactor exceeding of which leads to significant local overheating of the centers - thermal explosion. The temperature distribution with the local reaction centers is qualitatively different from the granule temperature, calculated in the homogeneous approximation. It is shown that, in contrast to the homogeneous approximation, the

  18. Turing instability in reaction-diffusion models on complex networks

    Ide, Yusuke; Izuhara, Hirofumi; Machida, Takuya


    In this paper, the Turing instability in reaction-diffusion models defined on complex networks is studied. Here, we focus on three types of models which generate complex networks, i.e. the Erdős-Rényi, the Watts-Strogatz, and the threshold network models. From analysis of the Laplacian matrices of graphs generated by these models, we numerically reveal that stable and unstable regions of a homogeneous steady state on the parameter space of two diffusion coefficients completely differ, depending on the network architecture. In addition, we theoretically discuss the stable and unstable regions in the cases of regular enhanced ring lattices which include regular circles, and networks generated by the threshold network model when the number of vertices is large enough.

  19. Developed Hybrid Model for Propylene Polymerisation at Optimum Reaction Conditions

    Mohammad Jakir Hossain Khan


    Full Text Available A statistical model combined with CFD (computational fluid dynamic method was used to explain the detailed phenomena of the process parameters, and a series of experiments were carried out for propylene polymerisation by varying the feed gas composition, reaction initiation temperature, and system pressure, in a fluidised bed catalytic reactor. The propylene polymerisation rate per pass was considered the response to the analysis. Response surface methodology (RSM, with a full factorial central composite experimental design, was applied to develop the model. In this study, analysis of variance (ANOVA indicated an acceptable value for the coefficient of determination and a suitable estimation of a second-order regression model. For better justification, results were also described through a three-dimensional (3D response surface and a related two-dimensional (2D contour plot. These 3D and 2D response analyses provided significant and easy to understand findings on the effect of all the considered process variables on expected findings. To diagnose the model adequacy, the mathematical relationship between the process variables and the extent of polymer conversion was established through the combination of CFD with statistical tools. All the tests showed that the model is an excellent fit with the experimental validation. The maximum extent of polymer conversion per pass was 5.98% at the set time period and with consistent catalyst and co-catalyst feed rates. The optimum conditions for maximum polymerisation was found at reaction temperature (RT 75 °C, system pressure (SP 25 bar, and 75% monomer concentration (MC. The hydrogen percentage was kept fixed at all times. The coefficient of correlation for reaction temperature, system pressure, and monomer concentration ratio, was found to be 0.932. Thus, the experimental results and model predicted values were a reliable fit at optimum process conditions. Detailed and adaptable CFD results were capable

  20. The assessment of the performance of covariance-based structural equation modeling and partial least square path modeling

    Aimran, Ahmad Nazim; Ahmad, Sabri; Afthanorhan, Asyraf; Awang, Zainudin


    Structural equation modeling (SEM) is the second generation statistical analysis technique developed for analyzing the inter-relationships among multiple variables in a model. Previous studies have shown that there seemed to be at least an implicit agreement about the factors that should drive the choice between covariance-based structural equation modeling (CB-SEM) and partial least square path modeling (PLS-PM). PLS-PM appears to be the preferred method by previous scholars because of its less stringent assumption and the need to avoid the perceived difficulties in CB-SEM. Along with this issue has been the increasing debate among researchers on the use of CB-SEM and PLS-PM in studies. The present study intends to assess the performance of CB-SEM and PLS-PM as a confirmatory study in which the findings will contribute to the body of knowledge of SEM. Maximum likelihood (ML) was chosen as the estimator for CB-SEM and was expected to be more powerful than PLS-PM. Based on the balanced experimental design, the multivariate normal data with specified population parameter and sample sizes were generated using Pro-Active Monte Carlo simulation, and the data were analyzed using AMOS for CB-SEM and SmartPLS for PLS-PM. Comparative Bias Index (CBI), construct relationship, average variance extracted (AVE), composite reliability (CR), and Fornell-Larcker criterion were used to study the consequence of each estimator. The findings conclude that CB-SEM performed notably better than PLS-PM in estimation for large sample size (100 and above), particularly in terms of estimations accuracy and consistency.

  1. Bayesian inference of chemical kinetic models from proposed reactions

    Galagali, Nikhil


    © 2014 Elsevier Ltd. Bayesian inference provides a natural framework for combining experimental data with prior knowledge to develop chemical kinetic models and quantify the associated uncertainties, not only in parameter values but also in model structure. Most existing applications of Bayesian model selection methods to chemical kinetics have been limited to comparisons among a small set of models, however. The significant computational cost of evaluating posterior model probabilities renders traditional Bayesian methods infeasible when the model space becomes large. We present a new framework for tractable Bayesian model inference and uncertainty quantification using a large number of systematically generated model hypotheses. The approach involves imposing point-mass mixture priors over rate constants and exploring the resulting posterior distribution using an adaptive Markov chain Monte Carlo method. The posterior samples are used to identify plausible models, to quantify rate constant uncertainties, and to extract key diagnostic information about model structure-such as the reactions and operating pathways most strongly supported by the data. We provide numerical demonstrations of the proposed framework by inferring kinetic models for catalytic steam and dry reforming of methane using available experimental data.

  2. A New Geochemical Reaction Model for Groundwater Systems


    Through a survey of the literature on geology, hydrogeology and hydrogeochemistry, this paper presents a hydrogeochemical model for the groundwater system in a dross-dumping area of the Shandong Aluminium Plant. It is considered that the groundwater-bearing medium is a mineral aggregate and that the interactions between groundwater and the groundwater-bearing medium can be described as a series of geochemical reactions. On that basis, the principle of minimum energy and the equations of mass balance, electron balance and electric neutrality are applied to construct a linear programming mathematical model for the calculation of mass transfer between water and rock with the simplex method.

  3. Forced thermal cycling of catalytic reactions: experiments and modelling

    Jensen, Søren; Olsen, Jakob Lind; Thorsteinsson, Sune;


    Recent studies of catalytic reactions subjected to fast forced temperature oscillations have revealed a rate enhancement increasing with temperature oscillation frequency. We present detailed studies of the rate enhancement up to frequencies of 2.5 Hz. A maximum in the rate enhancement is observed...... at about 1 Hz. A model for the rate enhancement that includes the surface kinetics and the dynamic partial pressure variations in the reactor is introduced. The model predicts a levelling off of the rate enhancement with frequency at about 1 Hz. The experimentally observed decrease above 1 Hz is explained...... by dynamic thermal limitations of the reactor. (c) 2007 Elsevier B.V. All rights reserved....

  4. Universal model for exoergic bimolecular reactions and inelastic processes

    Gao, Bo


    From a rigorous multichannel quantum-defect formulation of bimolecular processes, we derive a fully quantal and analytic model for the total rate of exoergic bimolecular reactions and/or inelastic processes that is applicable over a wide range of temperatures including the ultracold regime. The theory establishes a connection between the ultracold chemistry and the regular chemistry by showing that the same theory that gives the quantum threshold behavior agrees with the classical Gorin model at higher temperatures. In between, it predicts that the rates for identical bosonic molecules and distinguishable molecules would first decrease with temperature outside of the Wigner threshold region, before rising after a minimum is reached.

  5. A discrete model to study reaction-diffusion-mechanics systems.

    Weise, Louis D; Nash, Martyn P; Panfilov, Alexander V


    This article introduces a discrete reaction-diffusion-mechanics (dRDM) model to study the effects of deformation on reaction-diffusion (RD) processes. The dRDM framework employs a FitzHugh-Nagumo type RD model coupled to a mass-lattice model, that undergoes finite deformations. The dRDM model describes a material whose elastic properties are described by a generalized Hooke's law for finite deformations (Seth material). Numerically, the dRDM approach combines a finite difference approach for the RD equations with a Verlet integration scheme for the equations of the mass-lattice system. Using this framework results were reproduced on self-organized pacemaking activity that have been previously found with a continuous RD mechanics model. Mechanisms that determine the period of pacemakers and its dependency on the medium size are identified. Finally it is shown how the drift direction of pacemakers in RDM systems is related to the spatial distribution of deformation and curvature effects.

  6. A discrete model to study reaction-diffusion-mechanics systems.

    Louis D Weise

    Full Text Available This article introduces a discrete reaction-diffusion-mechanics (dRDM model to study the effects of deformation on reaction-diffusion (RD processes. The dRDM framework employs a FitzHugh-Nagumo type RD model coupled to a mass-lattice model, that undergoes finite deformations. The dRDM model describes a material whose elastic properties are described by a generalized Hooke's law for finite deformations (Seth material. Numerically, the dRDM approach combines a finite difference approach for the RD equations with a Verlet integration scheme for the equations of the mass-lattice system. Using this framework results were reproduced on self-organized pacemaking activity that have been previously found with a continuous RD mechanics model. Mechanisms that determine the period of pacemakers and its dependency on the medium size are identified. Finally it is shown how the drift direction of pacemakers in RDM systems is related to the spatial distribution of deformation and curvature effects.

  7. A Path Model of Expressive Vocabulary Skills in Initially Preverbal Preschool Children with Autism Spectrum Disorder.

    McDaniel, Jena; Yoder, Paul; Watson, Linda R


    We examined direct and indirect paths involving receptive vocabulary and diversity of key consonants used in communication (DKCC) to improve understanding of why previously identified value-added predictors are associated with later expressive vocabulary for initially preverbal children with autism spectrum disorder (ASD; n = 87). Intentional communication, DKCC, and parent linguistic responses accounted for unique variance in later expressive vocabulary when controlling for mid-point receptive vocabulary, but responding to joint attention did not. We did not confirm any indirect paths through mid-point receptive vocabulary. DKCC mediated the association between intentional communication and expressive vocabulary. Further research is needed to replicate the findings, test potentially causal relations, and provide a specific sequence of intervention targets for preverbal children with ASD.

  8. Reactions of Lignin Model Compounds in Ionic Liquids

    Holladay, John E.; Binder, Joseph B.; Gray, Michel J.; White, James F.; Zhang, Z. Conrad


    Lignin, a readily available form of biomass, awaits novel chemistry for converting it to valuable aromatic chemicals. Recent work has demonstrated that ionic liquids are excellent solvents for processing woody biomass and lignin. Seeking to exploit ionic liquids as media for depolymerization of lignin, we investigated reactions of lignin model compounds in these solvents. Using Brønsted acid catalysts in 1-ethyl-3-methylimidazolium triflate at moderate temperatures, we obtained up to 11.6% yield of the dealkylation product guaiacol from the model compound eugenol and cleaved phenethyl phenyl ether, a model for lignin ethers. Despite these successes, acid catalysis failed in dealkylation of the unsaturated model compound 4-ethylguaiacol and did not produce monomeric products from organosolv lignin, demonstrating that further work is required to understand the complex chemistry of lignin depolymerization.

  9. Least Squares Support Vector Machine Based Real-Time Fault Diagnosis Model for Gas Path Parameters of Aero Engines

    WANG Xu-hui; HUANG Sheng-guo; WANG Ye; LIU Yong-jian; SHU Ping


    Least squares support vector machine (LS-SVM) is applied in gas path fault diagnosis for aero engines.Firstly,the deviation data of engine cruise are analyzed.Then,model selection is conducted using pattern search method.Finally,by decoding aircraft communication addressing and reporting system (ACARS) report,a real-time cruise data set is acquired,and the diagnosis model is adopted to process data.In contrast to the radial basis function (RBF) neutral network,LS-SVM is more suitable for real-time diagnosis of gas turbine engine.

  10. Analysis of rain fade duration models for Earth-to-satellite path based on data measured in Malaysia

    Dao, Hassan; Rafiqul, Islam Md; Al-Khateeb, Khalid A. S.


    Statistical analysis of rain fade duration is crucial information for system engineer to design and plan a fade mitigation technique (FMT) for the satellite communication system. An investigation is carried out based on data measured of one year period in Kuala Lumpur, Malaysia from satellite path of MEASAT3. This paper presents statistical analysis of measured fade duration on high elevation angle (77.4°) in Ku-band compared to three prediction models of fade duration. It is found that none of the models could predict measured fade duration distribution accurately.

  11. Local path planning method of the self-propelled model based on reinforcement learning in complex conditions

    Yang, Yi; Pang, Yongjie; Li, Hongwei; Zhang, Rubo


    Conducting hydrodynamic and physical motion simulation tests using a large-scale self-propelled model under actual wave conditions is an important means for researching environmental adaptability of ships. During the navigation test of the self-propelled model, the complex environment including various port facilities, navigation facilities, and the ships nearby must be considered carefully, because in this dense environment the impact of sea waves and winds on the model is particularly significant. In order to improve the security of the self-propelled model, this paper introduces the Q learning based on reinforcement learning combined with chaotic ideas for the model's collision avoidance, in order to improve the reliability of the local path planning. Simulation and sea test results show that this algorithm is a better solution for collision avoidance of the self navigation model under the interference of sea winds and waves with good adaptability.

  12. 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.

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


    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.

  13. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

    Zhang, Fan [ORNL; Yeh, Gour-Tsyh [University of Central Florida, Orlando; Parker, Jack C [ORNL; Brooks, Scott C [ORNL; Pace, Molly [ORNL; Kim, Young Jin [ORNL; Jardine, Philip M [ORNL; Watson, David B [ORNL


    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing NE equilibrium reactions and a set of reactive transport equations of M-NE kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

  14. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C.; Brooks, Scott C.; Pace, Molly N.; Kim, Young-Jin; Jardine, Philip M.; Watson, David B.


    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing NE equilibrium reactions and a set of reactive transport equations of M- NE kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

  15. Predictors and mediators of add-on mirtazapine-induced cognitive enhancement in schizophrenia--a path model investigation.

    Stenberg, Jan-Henry; Terevnikov, Viacheslav; Joffe, Marina; Tiihonen, Jari; Chukhin, Evgeny; Burkin, Mark; Joffe, Grigori


    We aimed to evaluate predictors and mediators of enhancing effect of adjunctive mirtazapine on cognition in schizophrenia. Patients with difficult-to-treat schizophrenia received either mirtazapine (n = 19) or placebo (n = 18) in a double-blind fashion for six weeks. Mirtazapine outperformed placebo on the Block Design and Stroop Dots. In the present subsidiary study, factors underlying this difference were explored with Path Analysis. Add-on mirtazapine had an independent enhancing effect on the Block Design-measured visuo-spatial functioning. Further, this effect was mediated via changes in positive, depressive and parkinsonism symptoms, but not in negative symptoms. This effect was predicted by higher doses of FGAs, longer duration of illness and lower initial Block Design scores. Path Analysis model fit was good. Mirtazapine may have direct and indirect favorable effects on visuo-spatial functioning, but further research is needed. Path analysis may be a feasible statistical method for further research of neurocognition in psychopharmacological interventions in schizophrenia. This article is part of a Special Issue entitled 'Cognitive Enhancers'. Copyright © 2012 Elsevier Ltd. All rights reserved.

  16. Evaluation of the existing triple point path models with new experimental data: proposal of an original empirical formulation

    Boutillier, J.; Ehrhardt, L.; De Mezzo, S.; Deck, C.; Magnan, P.; Naz, P.; Willinger, R.


    With the increasing use of improvised explosive devices (IEDs), the need for better mitigation, either for building integrity or for personal security, increases in importance. Before focusing on the interaction of the shock wave with a target and the potential associated damage, knowledge must be acquired regarding the nature of the blast threat, i.e., the pressure-time history. This requirement motivates gaining further insight into the triple point (TP) path, in order to know precisely which regime the target will encounter (simple reflection or Mach reflection). Within this context, the purpose of this study is to evaluate three existing TP path empirical models, which in turn are used in other empirical models for the determination of the pressure profile. These three TP models are the empirical function of Kinney, the Unified Facilities Criteria (UFC) curves, and the model of the Natural Resources Defense Council (NRDC). As discrepancies are observed between these models, new experimental data were obtained to test their reliability and a new promising formulation is proposed for scaled heights of burst ranging from 24.6-172.9 cm/kg^{1/3}.

  17. Mechanical reaction-diffusion model for bacterial population dynamics

    Ngamsaad, Waipot


    The effect of mechanical interaction between cells on the spreading of bacterial population was investigated in one-dimensional space. A nonlinear reaction-diffusion equation has been formulated as a model for this dynamics. In this model, the bacterial cells are treated as the rod-like particles that interact, when contacting each other, through the hard-core repulsion. The repulsion introduces the exclusion process that causes the fast diffusion in bacterial population at high density. The propagation of the bacterial density as the traveling wave front in long time behavior has been analyzed. The analytical result reveals that the front speed is enhanced by the exclusion process---and its value depends on the packing fraction of cell. The numerical solutions of the model have been solved to confirm this prediction.

  18. A time-delayed model for radiation reaction in electrodynamics

    Faci, Sofiane; Satheeshkumar, V H


    The dynamics of a radiating charge is one of the oldest unsettled problems in classical physics. The standard Lorentz-Abraham-Dirac (LAD) equation of motion is known to suffer from several pathologies and ambiguities. This paper briefly reviews these issues, and reports on a new model that fixes these difficulties in a natural way. This model is based on a hypothesis that there is an infinitesimal time delay between action and reaction. This can be related to Feynman's regularization scheme, leading to a quasi-local QED with a natural UV cutoff, hence without the need for renormalization as the divergences are absent. Besides leading to a pathology-free equation of motion, the new model predicts a modification of the Larmor formula that is testable with current and near future ultra-intense lasers.

  19. Reaction times to weak test lights. [psychophysics biological model

    Wandell, B. A.; Ahumada, P.; Welsh, D.


    Maloney and Wandell (1984) describe a model of the response of a single visual channel to weak test lights. The initial channel response is a linearly filtered version of the stimulus. The filter output is randomly sampled over time. Each time a sample occurs there is some probability increasing with the magnitude of the sampled response - that a discrete detection event is generated. Maloney and Wandell derive the statistics of the detection events. In this paper a test is conducted of the hypothesis that the reaction time responses to the presence of a weak test light are initiated at the first detection event. This makes it possible to extend the application of the model to lights that are slightly above threshold, but still within the linear operating range of the visual system. A parameter-free prediction of the model proposed by Maloney and Wandell for lights detected by this statistic is tested. The data are in agreement with the prediction.

  20. Modeling the Reactions of Energetic Materials in the Condensed Phase

    Fried, L E; Manaa, M R; Lewis, J P


    High explosive (HE) materials are unique for having a strong exothermic reactivity, which has made them desirable for both military and commercial applications. Although the history of HE materials is long, condensed-phase properties are poorly understood. Understanding the condensed-phase properties of HE materials is important for determining stability and performance. Information regarding HE material properties (for example, the physical, chemical, and mechanical behaviors of the constituents in plastic-bonded explosive, or PBX, formulations) is necessary in efficiently building the next generation of explosives as the quest for more powerful energetic materials (in terms of energy per volume) moves forward. In addition, understanding the reaction mechanisms has important ramifications in disposing of such materials safely and cheaply, as there exist vast stockpiles of HE materials with corresponding contamination of earth and groundwater at these sites, as well as a military testing sites The ability to model chemical reaction processes in condensed phase energetic materials is rapidly progressing. Chemical equilibrium modeling is a mature technique with some limitations. Progress in this area continues, but is hampered by a lack of knowledge of condensed phase reaction mechanisms and rates. Atomistic modeling is much more computationally intensive, and is currently limited to very short time scales. Nonetheless, this methodology promises to yield the first reliable insights into the condensed phase processes responsible for high explosive detonation. Further work is necessary to extend the timescales involved in atomistic simulations. Recent work in implementing thermostat methods appropriate to shocks may promise to overcome some of these difficulties. Most current work on energetic material reactivity assumes that electronically adiabatic processes dominate. The role of excited states is becoming clearer, however. These states are not accessible in perfect

  1. Systematic development of reduced reaction mechanisms for dynamic modeling

    Frenklach, M.; Kailasanath, K.; Oran, E. S.


    A method for systematically developing a reduced chemical reaction mechanism for dynamic modeling of chemically reactive flows is presented. The method is based on the postulate that if a reduced reaction mechanism faithfully describes the time evolution of both thermal and chain reaction processes characteristic of a more complete mechanism, then the reduced mechanism will describe the chemical processes in a chemically reacting flow with approximately the same degree of accuracy. Here this postulate is tested by producing a series of mechanisms of reduced accuracy, which are derived from a full detailed mechanism for methane-oxygen combustion. These mechanisms were then tested in a series of reactive flow calculations in which a large-amplitude sinusoidal perturbation is applied to a system that is initially quiescent and whose temperature is high enough to start ignition processes. Comparison of the results for systems with and without convective flow show that this approach produces reduced mechanisms that are useful for calculations of explosions and detonations. Extensions and applicability to flames are discussed.

  2. BlenX-based compositional modeling of complex reaction mechanisms

    Judit Zámborszky


    Full Text Available Molecular interactions are wired in a fascinating way resulting in complex behavior of biological systems. Theoretical modeling provides a useful framework for understanding the dynamics and the function of such networks. The complexity of the biological networks calls for conceptual tools that manage the combinatorial explosion of the set of possible interactions. A suitable conceptual tool to attack complexity is compositionality, already successfully used in the process algebra field to model computer systems. We rely on the BlenX programming language, originated by the beta-binders process calculus, to specify and simulate high-level descriptions of biological circuits. The Gillespie's stochastic framework of BlenX requires the decomposition of phenomenological functions into basic elementary reactions. Systematic unpacking of complex reaction mechanisms into BlenX templates is shown in this study. The estimation/derivation of missing parameters and the challenges emerging from compositional model building in stochastic process algebras are discussed. A biological example on circadian clock is presented as a case study of BlenX compositionality.

  3. Reaction-diffusion-branching models of stock price fluctuations

    Tang, Lei-Han; Tian, Guang-Shan

    Several models of stock trading (Bak et al., Physica A 246 (1997) 430.) are analyzed in analogy with one-dimensional, two-species reaction-diffusion-branching processes. Using heuristic and scaling arguments, we show that the short-time market price variation is subdiffusive with a Hurst exponent H=1/4. Biased diffusion towards the market price and blind-eyed copying lead to crossovers to the empirically observed random-walk behavior ( H=1/2) at long times. The calculated crossover forms and diffusion constants are shown to agree well with simulation data.

  4. Parametric pattern selection in a reaction-diffusion model.

    Michael Stich

    Full Text Available We compare spot patterns generated by Turing mechanisms with those generated by replication cascades, in a model one-dimensional reaction-diffusion system. We determine the stability region of spot solutions in parameter space as a function of a natural control parameter (feed-rate where degenerate patterns with different numbers of spots coexist for a fixed feed-rate. While it is possible to generate identical patterns via both mechanisms, we show that replication cascades lead to a wider choice of pattern profiles that can be selected through a tuning of the feed-rate, exploiting hysteresis and directionality effects of the different pattern pathways.

  5. Local Path Planning Method of the Self-propelled Model Based on Reinforcement Learning in Complex Conditions

    Yi Yang; Yongjie Pang; Hongwei Li; Rubo Zhang


    Conducting hydrodynamic and physical motion simulation tests using a large-scale self-propelled model under actual wave conditions is an important means for researching environmental adaptability of ships. During the navigation test of the self-propelled model, the complex environment including various port facilities, navigation facilities, and the ships nearby must be considered carefully, because in this dense environment the impact of sea waves and winds on the model is particularly significant. In order to improve the security of the self-propelled model, this paper introduces the Q learning based on reinforcement learning combined with chaotic ideas for the model’s collision avoidance, in order to improve the reliability of the local path planning. Simulation and sea test results show that this algorithm is a better solution for collision avoidance of the self navigation model under the interference of sea winds and waves with good adaptability.

  6. Many-body quantum dynamics by adiabatic path-integral molecular dynamics: Disordered Frenkel Kontorova models

    Krajewski, Florian R.; Müser, Martin H.


    The spectral density of quantum mechanical Frenkel Kontorova chains moving in disordered, external potentials is investigated by means of path-integral molecular dynamics. If the second moment of the embedding potential is well defined (roughness exponent H=0), there is one regime in which the chain is pinned (large masses m of chain particles) and one in which it is unpinned (small m). If the embedding potential can be classified as a random walk on large length scales ( H=1/2), then the chain is always pinned irrespective of the value of m. For H=1/2, two phonon-like branches appear in the spectra.

  7. Molecular attenuation and phase dispersion between 40 and 140-GHz for path models from different altitudes

    Liebe, H. J.; Welch, W. M.


    Radio wave propagation in the 40 to 140 GHz band through the first hundred kilometers of the atmosphere is strongly influenced by the microwave spectrum of oxygen (O2-MS). A unified treatment of molecular attenuation and phase dispersion is formulated. Results of molecular physics are translated into frequency, temperature, pressure, and magnetic field dependencies of a complex refractive index. The intensity distribution of the O2-MS undergoes several changes with increasing altitude. The influence of water vapor is discussed. Examples of computer plots are given as a function of altitude for homogeneous, zenith, and tangential path geometries. Molecular resonances of minor atmospheric gases are discussed briefly.

  8. Beyond transition state theory: accurate description of nuclear quantum effects on the rate and equilibrium constants of chemical reactions using Feynman path integrals.

    Vanícek, Jirí


    Nuclear tunneling and other nuclear quantum effects have been shown to play a significant role in molecules as large as enzymes even at physiological temperatures. I discuss how these quantum phenomena can be accounted for rigorously using Feynman path integrals in calculations of the equilibrium and kinetic isotope effects as well as of the temperature dependence of the rate constant. Because these calculations are extremely computationally demanding, special attention is devoted to increasing the computational efficiency by orders of magnitude by employing efficient path integral estimators.

  9. Stepwise kinetic equilibrium models of quantitative polymerase chain reaction

    Cobbs Gary


    Full Text Available Abstract Background Numerous models for use in interpreting quantitative PCR (qPCR data are present in recent literature. The most commonly used models assume the amplification in qPCR is exponential and fit an exponential model with a constant rate of increase to a select part of the curve. Kinetic theory may be used to model the annealing phase and does not assume constant efficiency of amplification. Mechanistic models describing the annealing phase with kinetic theory offer the most potential for accurate interpretation of qPCR data. Even so, they have not been thoroughly investigated and are rarely used for interpretation of qPCR data. New results for kinetic modeling of qPCR are presented. Results Two models are presented in which the efficiency of amplification is based on equilibrium solutions for the annealing phase of the qPCR process. Model 1 assumes annealing of complementary targets strands and annealing of target and primers are both reversible reactions and reach a dynamic equilibrium. Model 2 assumes all annealing reactions are nonreversible and equilibrium is static. Both models include the effect of primer concentration during the annealing phase. Analytic formulae are given for the equilibrium values of all single and double stranded molecules at the end of the annealing step. The equilibrium values are then used in a stepwise method to describe the whole qPCR process. Rate constants of kinetic models are the same for solutions that are identical except for possibly having different initial target concentrations. Analysis of qPCR curves from such solutions are thus analyzed by simultaneous non-linear curve fitting with the same rate constant values applying to all curves and each curve having a unique value for initial target concentration. The models were fit to two data sets for which the true initial target concentrations are known. Both models give better fit to observed qPCR data than other kinetic models present in the

  10. Quantum mechanics/molecular mechanics minimum free-energy path for accurate reaction energetics in solution and enzymes: Sequential sampling and optimization on the potential of mean force surface

    Hu, Hao; Lu, Zhenyu; Parks, Jerry M.; Burger, Steven K.; Yang, Weitao


    To accurately determine the reaction path and its energetics for enzymatic and solution-phase reactions, we present a sequential sampling and optimization approach that greatly enhances the efficiency of the ab initio quantum mechanics/molecular mechanics minimum free-energy path (QM/MM-MFEP) method. In the QM/MM-MFEP method, the thermodynamics of a complex reaction system is described by the potential of mean force (PMF) surface of the quantum mechanical (QM) subsystem with a small number of degrees of freedom, somewhat like describing a reaction process in the gas phase. The main computational cost of the QM/MM-MFEP method comes from the statistical sampling of conformations of the molecular mechanical (MM) subsystem required for the calculation of the QM PMF and its gradient. In our new sequential sampling and optimization approach, we aim to reduce the amount of MM sampling while still retaining the accuracy of the results by first carrying out MM phase-space sampling and then optimizing the QM subsystem in the fixed-size ensemble of MM conformations. The resulting QM optimized structures are then used to obtain more accurate sampling of the MM subsystem. This process of sequential MM sampling and QM optimization is iterated until convergence. The use of a fixed-size, finite MM conformational ensemble enables the precise evaluation of the QM potential of mean force and its gradient within the ensemble, thus circumventing the challenges associated with statistical averaging and significantly speeding up the convergence of the optimization process. To further improve the accuracy of the QM/MM-MFEP method, the reaction path potential method developed by Lu and Yang [Z. Lu and W. Yang, J. Chem. Phys. 121, 89 (2004)] is employed to describe the QM/MM electrostatic interactions in an approximate yet accurate way with a computational cost that is comparable to classical MM simulations. The new method was successfully applied to two example reaction processes, the

  11. The $^{136}$Xe + $^{208}$Pb reaction: A test of models of multi-nucleon transfer reactions

    Barrett, J S; Loveland, W; Zhu, S; Ayangeakaa, A D; Carpenter, M P; Greene, J P; Janssens, R V F; Lauritsen, T; McCutchan, E A; Sonzogni, A A; Chiara, C J; Harker, J L; Walters, W B


    The yields of over 200 projectile-like fragments (PLFs) and target-like fragments (TLFs) from the interaction of (E$_{c.m.}$=450 MeV) $^{136}$Xe with a thick target of $^{208}$Pb were measured using Gammasphere and off-line $\\gamma$-ray spectroscopy, giving a comprehensive picture of the production cross sections in this reaction.The measured yields were compared to predictions of the GRAZING model and the predictions of Zagrebaev and Greiner using a quantitative metric, the theory evaluation factor, {\\bf tef}. The GRAZING model predictions are adequate for describing the yields of nuclei near the target or projectile but grossly underestimate the yields of all other products. The predictions of Zagrebaev and Greiner correctly describe the magnitude and maxima of the observed TLF transfer cross sections for a wide range of transfers ($\\Delta$Z = -8 to $\\Delta$Z = +2). However for $\\Delta$Z =+4, the observed position of the maximum in the distribution is four neutrons richer than the predicted maximum. The pre...

  12. Japan Women's University Multi-Career Path Support Model for Female Researchers (abstract)

    Toyama, Yoshikazu; Kodate, Kashiko


    The overall goal of this project, funded by MEXT-Japan (Ministry of Education, Culture, Sports, and Technology), is to implement prototypical programs to foster and proactively engage female researchers. The project aims to provide comprehensive support for female researchers who wish to raise a family and pursue an academic career, and increase opportunities for female researchers to play more active roles. To achieve these objectives, three core actions are taken. First, with out-of-office/out-of-lab research support (ubiquitous research support), an assistant researcher is provided to help perform experiments while the ubiquitous researcher is out of the laboratory. A communication network is introduced to connect the laboratory with home to facilitate in-home research. Second, with human resources support, researchers' career paths, abilities, and experiences are accumulated in e-portfolios. This enables researchers coming from different fields of employment to pursue other career paths. Third, a follow-up survey and project planning are conducted. We believe through science education, science can be demystified, and made more accessible and fascinating for children. This would bode well for future generations. Alumni questionnaires show that 80% of respondents were very satisfied to have graduated with a science background.

  13. Feed drive modelling for the simulation of tool path tracking in multi-axis High Speed Machining

    Prévost, David; Lartigue, Claire; Dumur, Didier


    Within the context of High Speed Machining, it is essential to manage the trajectory generation to achieve both high surface quality and high productivity. As feed drives are one part of the set Machine tool - Numerical Controller, it is necessary to improve their performances to optimize feed drive dynamics during trajectory follow up. Hence, this paper deals with the modelling of the feed drive in the case of multi axis machining. This model can be used for the simulation of axis dynamics and tool-path tracking to tune parameters and optimize new frameworks of command strategies. A procedure of identification based on modern NC capabilities is presented and applied to industrial HSM centres. Efficiency of this modelling is assessed by experimental verifications on various representative trajectories. After implementing a Generalized Predictive Control, reliable simulations are performed thanks to the model. These simulations can then be used to tune parameters of this new framework according to the tool-pat...

  14. Exploring the role of mixing between subsurface flow paths on transit time distributions using a Lagrangian model

    Zehe, Erwin; Jackisch, Conrad; Rodriguez, Nicolas; Klaus, Julian


    Only a minute amount of global fresh water is stored in the unsaturated zone. Yet this tiny compartment controls soil microbial activity and associated trace gas emissions, transport and transformations of contaminants, plant productivity, runoff generation and groundwater recharge. To date, the processes controlling renewal and age of different fractions of the soil water stock are far from being understood. Current theories and process concepts were largely inferred either from over-simplified laboratory experiments, or non-exhaustive point observations and tracer data in the field. Tracer data provide key but yet integrated information about the distribution of travel times of the tracer molecules to a certain depth or on their travel depth distribution within a given time. We hence are able to observe the "effect" of soil structure i.e. partitioning of infiltrating water between fast preferential and slow flow paths and imperfect subsequent mixing between these flow paths in the subsurface and the related plant water uptake. However, we are not able to study the "cause" - because technologies for in-situ observations of flow, flow path topology and exchange processes at relevant interfaces have up to now not been at hand. In the present study we will make use of a Lagrangian model for subsurface water dynamics to explore how subsurface heterogeneity and mixing among different storage fractions affects residence time distribution in the unsaturated zone in a forward approach. Soil water is represented by particles of constant mass, which travel according to the Itô form of the Fokker Planck equation. The model concept builds on established soil physics by estimating the drift velocity and the diffusion term based on the soil water characteristics. The model has been shown to simulate capillary driven soil moisture dynamics in good accordance with a) the Richards equation and b) observed soil moisture data in different soil. The particle model may furthermore

  15. A robust methodology for kinetic model parameter estimation for biocatalytic reactions

    Al-Haque, Naweed; Andrade Santacoloma, Paloma de Gracia; Lima Afonso Neto, Watson;


    Effective estimation of parameters in biocatalytic reaction kinetic expressions are very important when building process models to enable evaluation of process technology options and alternative biocatalysts. The kinetic models used to describe enzyme-catalyzed reactions generally include several...

  16. Modelling of Serpentine Continuous Flow Polymerase Chain Reaction Microfluidics

    Abubakar Mohammed


    Full Text Available The continuous flow Polymerase Chain Reaction (PCR microfluidics DNA amplification device is a recent discovery aimed at eliminating the cyclic hold experienced while using the alternative stationary device.The Application of Computational Fluid Dynamics is increasingly growing and can help achieve optimal designs before actual fabrication. This paper presents a CFD modelling of a continuous flow serpentine PCR device with narrow and wider channels. There are two temperature regions at 950C and 600C for denaturation and annealing respectively. Extension is achieved along the middle of the channel at 720C owing to temperature gradient. The model require a pressure of 42.6KPa for a 30 cycle amplification.

  17. A reaction-diffusion model of human brain development.

    Julien Lefèvre


    Full Text Available Cortical folding exhibits both reproducibility and variability in the geometry and topology of its patterns. These two properties are obviously the result of the brain development that goes through local cellular and molecular interactions which have important consequences on the global shape of the cortex. Hypotheses to explain the convoluted aspect of the brain are still intensively debated and do not focus necessarily on the variability of folds. Here we propose a phenomenological model based on reaction-diffusion mechanisms involving Turing morphogens that are responsible for the differential growth of two types of areas, sulci (bottom of folds and gyri (top of folds. We use a finite element approach of our model that is able to compute the evolution of morphogens on any kind of surface and to deform it through an iterative process. Our model mimics the progressive folding of the cortical surface along foetal development. Moreover it reveals patterns of reproducibility when we look at several realizations of the model from a noisy initial condition. However this reproducibility must be tempered by the fact that a same fold engendered by the model can have different topological properties, in one or several parts. These two results on the reproducibility and variability of the model echo the sulcal roots theory that postulates the existence of anatomical entities around which the folding organizes itself. These sulcal roots would correspond to initial conditions in our model. Last but not least, the parameters of our model are able to produce different kinds of patterns that can be linked to developmental pathologies such as polymicrogyria and lissencephaly. The main significance of our model is that it proposes a first approach to the issue of reproducibility and variability of the cortical folding.

  18. 基于径方法的SCM信道建模与仿真%Construct-model and Simulation of the Spatial Channel Model Base on Paths

    张祥虎; 宋常建; 钟子发


    MIMO has been a key technology of the B3G/4G mobile communication system. SCM channel model based on paths can reflect the real time various speciality of MIMO channel, it can used in link level simulations of the B3G/4G system and owns some application value. This paper firstly analysed the basic theory of SCM channel model, secondly researched the ways of building chan- nel models based on paths in three cases and then realized simulations. Numerical simulations show that the envelope of SCM chan- nels' main paths is rayleigh distribution when there is no path of LOS and rice distribution when there is path of LOS, which is up to the real channel speciality.%MIMO已成为B3G/4G移动通信系统中的一项关键技术。基于径方法的SCM信道模型能很好的反映MIMO信道的实时变化特性,可用于B3G/4G系统的链路级仿真,具有一定应用价值。本文通过简要分析SCM信道模型的基本原理,重点研究了3种场景下基于径方法的信道建模并进行了仿真。结果表明:不存在直视径时SCM信道各主径包络服从瑞利分布,而存在直视径时则服从莱斯分布,完全符合实际信道特征。

  19. Path Dependence

    Madsen, Mogens Ove

    Begrebet Path Dependence blev oprindelig udviklet inden for New Institutionel Economics af bl.a. David, Arthur og North. Begrebet har spredt sig vidt i samfundsvidenskaberne og undergået en udvikling. Dette paper propagerer for at der er sket så en så omfattende udvikling af begrebet, at man nu kan...... tale om 1. og 2. generation af Path Dependence begrebet. Den nyeste udvikling af begrebet har relevans for metodologi-diskusionerne i relation til Keynes...

  20. Theory and modeling of the magnetic field measurement in LISA PathFinder

    Diaz-Aguilo, M; Lobo, A


    The magnetic diagnostics subsystem of the LISA Technology Package (LTP) on board the LISA PathFinder (LPF) spacecraft includes a set of four tri-axial fluxgate magnetometers, intended to measure with high precision the magnetic field at their respective positions. However, their readouts do not provide a direct measurement of the magnetic field at the positions of the test masses, and hence an interpolation method must be designed and implemented to obtain the values of the magnetic field at these positions. However, such interpolation process faces serious difficulties. Indeed, the size of the interpolation region is excessive for a linear interpolation to be reliable while, on the other hand, the number of magnetometer channels does not provide sufficient data to go beyond the linear approximation. We describe an alternative method to address this issue, by means of neural network algorithms. The key point in this approach is the ability of neural networks to learn from suitable training data representing t...

  1. The path inference filter: model-based low-latency map matching of probe vehicle data

    Hunter, Timothy; Abbeel, Pieter; Bayen, Alexandre


    Traffic congestion has a significant impact around the world. Building reliable and cost effective traffic monitoring systems is a prerequisite to addressing this phenomenon. Historically, traffic estimation has been limited to highways, and has relied on a static, dedicated sensing infrastructure such as loop detectors or cameras. In the case of city roads, this estimation problem is rather involved. This situation can be partly attributed to the lack of effective sensing in an urban setting. In this context, the most promising source of data is the GPS receiver in personal smartphones and commercial fleet vehicles. In this article, we present some algorithms that leverage this trend to produce some streaming data compatible with current state-of-the-art traffic estimation algorithms. These algorithms, which we will refer altogether as the path inference algorithm, have been implemented and deployed inside the Mobile Millennium system at Berkeley.

  2. Electron transfer reactions

    Cannon, R D


    Electron Transfer Reactions deals with the mechanisms of electron transfer reactions between metal ions in solution, as well as the electron exchange between atoms or molecules in either the gaseous or solid state. The book is divided into three parts. Part 1 covers the electron transfer between atoms and molecules in the gas state. Part 2 tackles the reaction paths of oxidation states and binuclear intermediates, as well as the mechanisms of electron transfer. Part 3 discusses the theories and models of the electron transfer process; theories and experiments involving bridged electron transfe

  3. Characterizing and Modelling Preferential Flow Path in Fractured Rock Aquifer: A Case Study at Shuangliou Fractured Rock Hydrogeology Research Site

    Hsu, Shih-Meng; Ke, Chien-Chung; Lo, Hung-Chieh; Lin, Yen-Tsu; Huang, Chi-Chao


    On the basis of a relatively sparse data set, fractured aquifers are difficult to be characterized and modelled. The three-dimensional configuration of transmissive fractures and fracture zones is needed to be understood flow heterogeneity in the aquifer. Innovative technologies for the improved interpretation are necessary to facilitate the development of accurate predictive models of ground-water flow and solute transport or to precisely estimate groundwater potential. To this end, this paper presents a procedure for characterizing and modelling preferential flow path in the fractured rock aquifer carried out at Fractured Rock Hydrogeology Research Site in Shuangliou Forest Recreation Area, Pingtung County, Southern Taiwan. The Shuangliou well field is a 40 by 30-meter area consisting of 6 wells (one geological well, one pumping well and four hydrogeological testing wells). The bedrock at the site is mainly composed of slate and intercalated by meta-sandstone. The overburden consists of about 5.6 m of gravel deposits. Based on results of 100 m geological borehole with borehole televiewer logging, vertical flow logging and full-wave sonic logging, high transmissivity zones in the bedrock underlying the well field were identified. One of transmissivity zone (at the depths of 30~32 m) and its fracture orientation(N56/54) selected for devising a multiple well system with 4 boreholes (borehole depths :45m, 35m, 35m and 25m, respectively), which were utilized to perform cross-borehole flow velocity data under the ambient flow and pumped flow conditions to identify preferential flow paths. Results from the cross-borehole test show the preferential flow pathways are corresponding to the predicted ones. Subsequently, a 3-D discrete fracture network model based on outcrop data was generated by the FracMan code. A validation between observed and simulated data has proved that the present model can accurately predict the hydrogeological properties (e.g., number of fractures

  4. A Reaction-Diffusion Model of Cholinergic Retinal Waves

    Lansdell, Benjamin; Ford, Kevin; Kutz, J. Nathan


    Prior to receiving visual stimuli, spontaneous, correlated activity in the retina, called retinal waves, drives activity-dependent developmental programs. Early-stage waves mediated by acetylcholine (ACh) manifest as slow, spreading bursts of action potentials. They are believed to be initiated by the spontaneous firing of Starburst Amacrine Cells (SACs), whose dense, recurrent connectivity then propagates this activity laterally. Their inter-wave interval and shifting wave boundaries are the result of the slow after-hyperpolarization of the SACs creating an evolving mosaic of recruitable and refractory cells, which can and cannot participate in waves, respectively. Recent evidence suggests that cholinergic waves may be modulated by the extracellular concentration of ACh. Here, we construct a simplified, biophysically consistent, reaction-diffusion model of cholinergic retinal waves capable of recapitulating wave dynamics observed in mice retina recordings. The dense, recurrent connectivity of SACs is modeled through local, excitatory coupling occurring via the volume release and diffusion of ACh. In addition to simulation, we are thus able to use non-linear wave theory to connect wave features to underlying physiological parameters, making the model useful in determining appropriate pharmacological manipulations to experimentally produce waves of a prescribed spatiotemporal character. The model is used to determine how ACh mediated connectivity may modulate wave activity, and how parameters such as the spontaneous activation rate and sAHP refractory period contribute to critical wave size variability. PMID:25474327

  5. An Equilibrium-Based Model of Gas Reaction and Detonation

    Trowbridge, L.D.


    During gaseous diffusion plant operations, conditions leading to the formation of flammable gas mixtures may occasionally arise. Currently, these could consist of the evaporative coolant CFC-114 and fluorinating agents such as F2 and ClF3. Replacement of CFC-114 with a non-ozone-depleting substitute is planned. Consequently, in the future, the substitute coolant must also be considered as a potential fuel in flammable gas mixtures. Two questions of practical interest arise: (1) can a particular mixture sustain and propagate a flame if ignited, and (2) what is the maximum pressure that can be generated by the burning (and possibly exploding) gas mixture, should it ignite? Experimental data on these systems, particularly for the newer coolant candidates, are limited. To assist in answering these questions, a mathematical model was developed to serve as a tool for predicting the potential detonation pressures and for estimating the composition limits of flammability for these systems based on empirical correlations between gas mixture thermodynamics and flammability for known systems. The present model uses the thermodynamic equilibrium to determine the reaction endpoint of a reactive gas mixture and uses detonation theory to estimate an upper bound to the pressure that could be generated upon ignition. The model described and documented in this report is an extended version of related models developed in 1992 and 1999.

  6. Three-Body Model Analysis of Subbarrier alpha Transfer Reaction

    Fukui, Tokuro; Yahiro, Masanobu


    Subbarrier alpha transfer reaction 13C(6Li,d)17O(6.356 MeV, 1/2+) at 3.6 MeV is analyzed with a alpha + d + 13C three-body model, and the asymptotic normalization coefficient (ANC) for alpha + 13C --> 17O(6.356 MeV, 1/2+), which essentially determines the reaction rate of 13C(alpha,n)16O, is extracted. Breakup effects of 6Li in the initial channel and those of 17O in the final channel are investigated with the continuum-discretized coupled-channels method (CDCC). The former is found to have a large back-coupling to the elastic channel, while the latter turns out significantly small. The transfer cross section calculated with Born approximation to the transition operator, including breakup states of 6Li, gives (C_{alpha 13C}{17O*})^2 =1.03 \\pm 0.29 fm^{-1}. This result is consistent with the value obtained by the previous DWBA calculation.

  7. A multi-pathway model for Photosynthetic reaction center

    Qin, M; Yi, X X


    Charge separation in light-harvesting complexes occurs in a pair of tightly coupled chlorophylls at the heart of photosynthetic reaction centers of both plants and bacteria. Recently it has been shown that quantum coherence can, in principle, enhance the efficiency of a solar cell, working like a quantum heat engine (QHE). Here, we propose a biological quantum heat engine (BQHE) motivated by Photosystem {\\rm II} reaction center (PS{\\rm II} RC) to describe the charge separation. Our model mainly considers two charge-separation pathways more than that in the published literature. The two pathways can interfere via cross-couplings and work together to enhance the charge-separation yields. We explore how these cross-couplings increase the current and voltage of the charge separation and discuss the advantages of multiple pathways in terms of current and power. The robustness of the BQHE against the charge recombination in natural PS{\\rm II} RC and dephasing induced by environments is also explored, and extension ...

  8. Tracer-aided modelling to explore non-linearities in flow paths, hydrological connectivity and faecal contamination risk

    Neill, A. J.; Tetzlaff, D.; Strachan, N.; Soulsby, C.


    The non-linearities of runoff generation processes are strongly influenced by the connectivity of hillslopes and channel networks, particularly where overland flow is an important runoff mechanism. Despite major advances in understanding hydrological connectivity and runoff generation, the role of connectivity in the contamination of potable water supplies by faecal pathogens from grazing animals remains unclear. This is a water quality issue with serious implications for public health. Here, we sought to understand the dynamics of hydrological connectivity, flow paths and linked faecal pathogen transport in a montane catchment in Scotland with high deer populations. We firstly calibrated, within an uncertainty framework, a parsimonious tracer-aided hydrological model to daily discharge and stream isotope data. The model, developed on the basis of past empirical and tracer studies, conceptualises the catchment as three interacting hydrological source areas (dynamic saturation zone, dynamic hillslope, and groundwater) for which water fluxes, water ages and storage-based connectivity can be simulated. We next coupled several faecal indicator organism (FIO; a common indicator of faecal pathogen contamination) behaviour and transport schemes to the robust hydrological models. A further calibration was then undertaken based on the ability of each coupled model to simulate daily FIO concentrations. This gave us a final set of coupled behavioural models from which we explored how in-stream FIO dynamics could be related to the changing connectivity between the three hydrological source areas, flow paths, water ages and consequent dominant runoff generation processes. We found that high levels of FIOs were transient and episodic, and strongly correlated with periods of high connectivity through overland flow. This non-linearity in connectivity and FIO flux was successfully captured within our dynamic, tracer-aided hydrological model.

  9. Small-scale behaviour in deterministic reaction models

    Politi, Paolo [Istituto dei Sistemi Complessi, Consiglio Nazionale delle Ricerche, Via Madonna del Piano 10, 50019 Sesto Fiorentino (Italy); Ben-Avraham, Daniel, E-mail: paolo.politi@isc.cnr.i, E-mail: benavraham@clarkson.ed [Physics Department, Clarkson University, Potsdam, NY 13699-5820 (United States)


    In a recent paper published in this journal (2009 J. Phys. A: Math. Theor. 42 495004) we studied a one-dimensional particles system where nearest particles attract with a force inversely proportional to a power {alpha} of their distance and coalesce upon encounter. Numerics yielded a distribution function h(z) for the gap between neighbouring particles, with h(z) {approx} z{sup {beta}({alpha})} for small z and {beta}({alpha}) > {alpha}. We can now prove analytically that in the strict limit of z {yields} 0, {beta} = {alpha} for {alpha} > 0, corresponding to the mean-field result, and we compute the length scale where the mean field breaks down. More generally, in that same limit correlations are negligible for any similar reaction model where attractive forces diverge with vanishing distance. The actual meaning of the measured exponent {beta}({alpha}) remains an open question.

  10. a Model Study of Complex Behavior in the Belousov - Reaction.

    Lindberg, David Mark


    We have studied the complex oscillatory behavior in a model of the Belousov-Zhabotinskii (BZ) reaction in a continuously-fed stirred tank reactor (CSTR). The model consisted of a set of nonlinear ordinary differential equations derived from a reduced mechanism of the chemical system. These equations were integrated numerically on a computer, which yielded the concentrations of the constituent chemicals as functions of time. In addition, solutions were tracked as functions of a single parameter, the stability of the solutions was determined, and bifurcations of the solutions were located and studied. The intent of this study was to use this BZ model to explore further a region of complex oscillatory behavior found in experimental investigations, the most thorough of which revealed an alternating periodic-chaotic (P-C) sequence of states. A P-C sequence was discovered in the model which showed the same qualitative features as the experimental sequence. In order to better understand the P-C sequence, a detailed study was conducted in the vicinity of the P-C sequence, with two experimentally accessible parameters as control variables. This study mapped out the bifurcation sets, and included examination of the dynamics of the stable periodic, unstable periodic, and chaotic oscillatory motion. Observations made from the model results revealed a rough symmetry which suggests a new way of looking at the P-C sequence. Other nonlinear phenomena uncovered in the model were boundary and interior crises, several codimension-two bifurcations, and similarities in the shapes of areas of stability for periodic orbits in two-parameter space. Each earlier model study of this complex region involved only a limited one-parameter scan and had limited success in producing agreement with experiments. In contrast, for those regions of complex behavior that have been studied experimentally, the observations agree qualitatively with our model results. Several new predictions of the model

  11. MARMOSET: The Path from LHC Data to the New Standard Model via On-Shell Effective Theories

    Arkani-Hamed, N; Mrenna, S; Schuster, P; Thaler, J; Toro, N; Wang, L T; Arkani-Hamed, Nima; Knuteson, Bruce; Mrenna, Stephen; Schuster, Philip; Thaler, Jesse; Toro, Natalia; Wang, Lian-Tao


    We describe a coherent strategy and set of tools for reconstructing the fundamental theory of the TeV scale from LHC data. We show that On-Shell Effective Theories (OSETs) effectively characterize hadron collider data in terms of masses, production cross sections, and decay modes of candidate new particles. An OSET description of the data strongly constrains the underlying new physics, and sharply motivates the construction of its Lagrangian. Simulating OSETs allows efficient analysis of new-physics signals, especially when they arise from complicated production and decay topologies. To this end, we present MARMOSET, a Monte Carlo tool for simulating the OSET version of essentially any new-physics model. MARMOSET enables rapid testing of theoretical hypotheses suggested by both data and model-building intuition, which together chart a path to the underlying theory. We illustrate this process by working through a number of data challenges, where the most important features of TeV-scale physics are reconstructe...

  12. Fission cross section calculations for 209Bi target nucleus based on fission reaction models in high energy regions

    Kaplan Abdullah


    Full Text Available Implementation of projects of new generation nuclear power plants requires the solving of material science and technological issues in developing of reactor materials. Melts of heavy metals (Pb, Bi and Pb-Bi due to their nuclear and thermophysical properties, are the candidate coolants for fast reactors and accelerator-driven systems (ADS. In this study, α, γ, p, n and 3He induced fission cross section calculations for 209Bi target nucleus at high-energy regions for (α,f, (γ,f, (p,f, (n,f and (3He,f reactions have been investigated using different fission reaction models. Mamdouh Table, Sierk, Rotating Liquid Drop and Fission Path models of theoretical fission barriers of TALYS 1.6 code have been used for the fission cross section calculations. The calculated results have been compared with the experimental data taken from the EXFOR database. TALYS 1.6 Sierk model calculations exhibit generally good agreement with the experimental measurements for all reactions used in this study.

  13. Collectivism culture, HIV stigma and social network support in Anhui, China: a path analytic model.

    Zang, Chunpeng; Guida, Jennifer; Sun, Yehuan; Liu, Hongjie


    HIV stigma is rooted in culture and, therefore, it is essential to investigate it within the context of culture. The objective of this study was to examine the interrelationships among individualism-collectivism, HIV stigma, and social network support. A social network study was conducted among 118 people living with HIVAIDS in China, who were infected by commercial plasma donation, a nonstigmatized behavior. The Individualism-Collectivism Interpersonal Assessment Inventory (ICIAI) was used to measure cultural norms and values in the context of three social groups, family members, friends, and neighbors. Path analyses revealed (1) a higher level of family ICIAI was significantly associated with a higher level of HIV self-stigma (β=0.32); (2) a higher level of friend ICIAI was associated with a lower level of self-stigma (β=-035); (3) neighbor ICIAI was associated with public stigma (β=-0.61); (4) self-stigman was associated with social support from neighbors (β=-0.27); and (5) public stigma was associated with social support from neighbors (β=-0.24). This study documents that HIV stigma may mediate the relationship between collectivist culture and social network support, providing an empirical basis for interventions to include aspects of culture into HIV intervention strategies.

  14. Modelling strong seismic ground motion: three-dimensional loading path versus wavefield polarization

    D'Avila, Maria Paola Santisi; Semblat, Jean-François


    Seismic waves due to strong earthquakes propagating in surficial soil layers may both reduce soil stiffness and increase the energy dissipation into the soil. To investigate seismic wave amplification in such cases, past studies have been devoted to one-directional shear wave propagation in a soil column (1D-propagation) considering one motion component only (1C-polarization). Three independent purely 1C computations may be performed ('1D-1C' approach) and directly superimposed in the case of weak motions (linear behaviour). This research aims at studying local site effects by considering seismic wave propagation in a 1-D soil profile accounting for the influence of the 3-D loading path and non-linear hysteretic behaviour of the soil. In the proposed '1D-3C' approach, the three components (3C-polarization) of the incident wave are simultaneously propagated into a horizontal multilayered soil. A 3-D non-linear constitutive relation for the soil is implemented in the framework of the Finite Element Method in th...

  15. A numerical model for predicting crack path and modes of damage in unidirectional metal matrix composites

    Bakuckas, J. G.; Tan, T. M.; Lau, A. C. W.; Awerbuch, J.


    A finite element-based numerical technique has been developed to simulate damage growth in unidirectional composites. This technique incorporates elastic-plastic analysis, micromechanics analysis, failure criteria, and a node splitting and node force relaxation algorithm to create crack surfaces. Any combination of fiber and matrix properties can be used. One of the salient features of this technique is that damage growth can be simulated without pre-specifying a crack path. In addition, multiple damage mechanisms in the forms of matrix cracking, fiber breakage, fiber-matrix debonding and plastic deformation are capable of occurring simultaneously. The prevailing failure mechanism and the damage (crack) growth direction are dictated by the instantaneous near-tip stress and strain fields. Once the failure mechanism and crack direction are determined, the crack is advanced via the node splitting and node force relaxation algorithm. Simulations of the damage growth process in center-slit boron/aluminum and silicon carbide/titanium unidirectional specimens were performed. The simulation results agreed quite well with the experimental observations.

  16. Campaign-level dynamic network modelling for spaceflight logistics for the flexible path concept

    Ho, Koki; de Weck, Olivier L.; Hoffman, Jeffrey A.; Shishko, Robert


    This paper develops a network optimization formulation for dynamic campaign-level space mission planning. Although many past space missions have been designed mainly from a mission-level perspective, a campaign-level perspective will be important for future space exploration. In order to find the optimal campaign-level space transportation architecture, a mixed-integer linear programming (MILP) formulation with a generalized multi-commodity flow and a time-expanded network is developed. Particularly, a new heuristics-based method, a partially static time-expanded network, is developed to provide a solution quickly. The developed method is applied to a case study containing human exploration of a near-Earth object (NEO) and Mars, related to the concept of the Flexible Path. The numerical results show that using the specific combinations of propulsion technologies, in-situ resource utilization (ISRU), and other space infrastructure elements can reduce the initial mass in low-Earth orbit (IMLEO) significantly. In addition, the case study results also show that we can achieve large IMLEO reduction by designing NEO and Mars missions together as a campaign compared with designing them separately owing to their common space infrastructure pre-deployment. This research will be an important step toward efficient and flexible campaign-level space mission planning.

  17. In silico toxicology models and databases as FDA Critical Path Initiative toolkits.

    Valerio, Luis G


    In silico toxicology methods are practical, evidence-based and high throughput, with varying accuracy. In silico approaches are of keen interest, not only to scientists in the private sector and to academic researchers worldwide, but also to the public. They are being increasingly evaluated and applied by regulators. Although there are foreseeable beneficial aspects--including maximising use of prior test data and the potential for minimising animal use for future toxicity testing--the primary use of in silico toxicology methods in the pharmaceutical sciences are as decision support information. It is possible for in silico toxicology methods to complement and strengthen the evidence for certain regulatory review processes, and to enhance risk management by supporting a more informed decision regarding priority setting for additional toxicological testing in research and product development. There are also several challenges with these continually evolving methods which clearly must be considered. This mini-review describes in silico methods that have been researched as Critical Path Initiative toolkits for predicting toxicities early in drug development based on prior knowledge derived from preclinical and clinical data at the US Food and Drug Administration, Center for Drug Evaluation and Research.

  18. In silico toxicology models and databases as FDA Critical Path Initiative toolkits

    Valerio Luis G


    Full Text Available Abstract In silico toxicology methods are practical, evidence-based and high throughput, with varying accuracy. In silico approaches are of keen interest, not only to scientists in the private sector and to academic researchers worldwide, but also to the public. They are being increasingly evaluated and applied by regulators. Although there are foreseeable beneficial aspects -- including maximising use of prior test data and the potential for minimising animal use for future toxicity testing -- the primary use of in silico toxicology methods in the pharmaceutical sciences are as decision support information. It is possible for in silico toxicology methods to complement and strengthen the evidence for certain regulatory review processes, and to enhance risk management by supporting a more informed decision regarding priority setting for additional toxicological testing in research and product development. There are also several challenges with these continually evolving methods which clearly must be considered. This mini-review describes in silico methods that have been researched as Critical Path Initiative toolkits for predicting toxicities early in drug development based on prior knowledge derived from preclinical and clinical data at the US Food and Drug Administration, Center for Drug Evaluation and Research.

  19. Pedestrian flow-path modeling to support tsunami evacuation and disaster relief planning in the U.S. Pacific Northwest

    Wood, Nathan J.; Jones, Jeanne M.; Schmidtlein, Mathew; Schelling, John; Frazier, T.


    Successful evacuations are critical to saving lives from future tsunamis. Pedestrian-evacuation modeling related to tsunami hazards primarily has focused on identifying areas and the number of people in these areas where successful evacuations are unlikely. Less attention has been paid to identifying evacuation pathways and population demand at assembly areas for at-risk individuals that may have sufficient time to evacuate. We use the neighboring coastal communities of Hoquiam, Aberdeen, and Cosmopolis (Washington, USA) and the local tsunami threat posed by Cascadia subduction zone earthquakes as a case study to explore the use of geospatial, least-cost-distance evacuation modeling for supporting evacuation outreach, response, and relief planning. We demonstrate an approach that uses geospatial evacuation modeling to (a) map the minimum pedestrian travel speeds to safety, the most efficient paths, and collective evacuation basins, (b) estimate the total number and demographic description of evacuees at predetermined assembly areas, and (c) determine which paths may be compromised due to earthquake-induced ground failure. Results suggest a wide range in the magnitude and type of evacuees at predetermined assembly areas and highlight parts of the communities with no readily accessible assembly area. Earthquake-induced ground failures could obstruct access to some assembly areas, cause evacuees to reroute to get to other assembly areas, and isolate some evacuees from relief personnel. Evacuation-modeling methods and results discussed here have implications and application to tsunami-evacuation outreach, training, response procedures, mitigation, and long-term land use planning to increase community resilience.

  20. Modeling the Liquid Water Transport in the Gas Diffusion Layer for Polymer Electrolyte Membrane Fuel Cells Using a Water Path Network

    Dietmar Gerteisen


    Full Text Available In order to model the liquid water transport in the porous materials used in polymer electrolyte membrane (PEM fuel cells, the pore network models are often applied. The presented model is a novel approach to further develop these models towards a percolation model that is based on the fiber structure rather than the pore structure. The developed algorithm determines the stable liquid water paths in the gas diffusion layer (GDL structure and the transitions from the paths to the subsequent paths. The obtained water path network represents the basis for the calculation of the percolation process with low calculation efforts. A good agreement with experimental capillary pressure-saturation curves and synchrotron liquid water visualization data from other literature sources is found. The oxygen diffusivity for the GDL with liquid water saturation at breakthrough reveals that the porosity is not a crucial factor for the limiting current density. An algorithm for condensation is included into the model, which shows that condensing water is redirecting the water path in the GDL, leading to an improved oxygen diffusion by a decreased breakthrough pressure and changed saturation distribution at breakthrough.

  1. A path model investigation of neurocognition, theory of mind, social competence, negative symptoms and real-world functioning in schizophrenia.

    Couture, Shannon M; Granholm, Eric L; Fish, Scott C


    Problems in real-world functioning are pervasive in schizophrenia and much recent effort has been devoted to uncovering factors which contribute to poor functioning. The goal of this study was to examine the role of four such factors: social cognition (theory of mind), neurocognition, negative symptoms, and functional capacity (social competence). 178 individuals with schizophrenia or schizoaffective disorder completed measures of theory of mind, neurocognition, negative symptoms, social competence, and self-reported functioning. Path models sought to determine the relationships among these variables. Theory of mind as indexed by the Hinting Task partially mediated the relationship between neurocognition and social competence, and negative symptoms and social competence demonstrated significant direct paths with self-reported functioning. Study results suggest theory of mind serves as an important mediator in addition to previously investigated social cognitive domains of emotional and social perception. The current study also highlights the need to determine variables which mediate the relationship between functional capacity and real-world functioning.

  2. A Path Model Investigation of Neurocognition, Theory of Mind, Social Competence, Negative Symptoms and Real-World Functioning in Schizophrenia

    Couture, Shannon M.; Granholm, Eric L.; Fish, Scott C.


    Problems in real-world functioning are pervasive in schizophrenia and much recent effort has been devoted to uncovering factors which contribute to poor functioning. The goal of this study was to examine the role of four such factors: social cognition (theory of mind), neurocognition, negative symptoms, and functional capacity (social competence). 178 individuals with schizophrenia or schizoaffective disorder completed measures of theory of mind, neurocognition, negative symptoms, social competence, and self-reported functioning. Path models sought to determine the relationships among these variables. Theory of mind as indexed by the Hinting Task partially mediated the relationship between neurocognition and social competence, and negative symptoms and social competence demonstrated significant direct paths with self-reported functioning. Study results suggest theory of mind serves as an important mediator in addition to previously investigated social cognitive domains of emotional and social perception. The current study also highlights the need to determine variables which mediate the relationship between functional capacity and real-world functioning. PMID:20965699

  3. Paths to nursing leadership.

    Bondas, Terese


    The aim was to explore why nurses enter nursing leadership and apply for a management position in health care. The study is part of a research programme in nursing leadership and evidence-based care. Nursing has not invested enough in the development of nursing leadership for the development of patient care. There is scarce research on nurses' motives and reasons for committing themselves to a career in nursing leadership. A strategic sample of 68 Finnish nurse leaders completed a semistructured questionnaire. Analytic induction was applied in an attempt to generate a theory. A theory, Paths to Nursing Leadership, is proposed for further research. Four different paths were found according to variations between the nurse leaders' education, primary commitment and situational factors. They are called the Path of Ideals, the Path of Chance, the Career Path and the Temporary Path. Situational factors and role models of good but also bad nursing leadership besides motivational and educational factors have played a significant role when Finnish nurses have entered nursing leadership. The educational requirements for nurse leaders and recruitment to nursing management positions need serious attention in order to develop a competent nursing leadership.

  4. Chemical Reaction and Flow Modeling in Fullerene and Nanotube Production

    Scott, Carl D.; Farhat, Samir; Greendyke, Robert B.


    The development of processes to produce fullerenes and carbon nanotubes has largely been empirical. Fullerenes were first discovered in the soot produced by laser ablation of graphite [1]and then in the soot of electric arc evaporated carbon. Techniques and conditions for producing larger and larger quantities of fullerenes depended mainly on trial and error empirical variations of these processes, with attempts to scale them up by using larger electrodes and targets and higher power. Various concepts of how fullerenes and carbon nanotubes were formed were put forth, but very little was done based on chemical kinetics of the reactions. This was mainly due to the complex mixture of species and complex nature of conditions in the reactors. Temperatures in the reactors varied from several thousand degrees Kelvin down to near room temperature. There are hundreds of species possible, ranging from atomic carbon to large clusters of carbonaceous soot, and metallic catalyst atoms to metal clusters, to complexes of metals and carbon. Most of the chemical kinetics of the reactions and the thermodynamic properties of clusters and complexes have only been approximated. In addition, flow conditions in the reactors are transient or unsteady, and three dimensional, with steep spatial gradients of temperature and species concentrations. All these factors make computational simulations of reactors very complex and challenging. This article addresses the development of the chemical reaction involved in fullerene production and extends this to production of carbon nanotubes by the laser ablation/oven process and by the electric arc evaporation process. In addition, the high-pressure carbon monoxide (HiPco) process is discussed. The article is in several parts. The first one addresses the thermochemical aspects of modeling; and considers the development of chemical rate equations, estimates of reaction rates, and thermodynamic properties where they are available. The second part

  5. Path Creation

    Karnøe, Peter; Garud, Raghu


    This paper employs path creation as a lens to follow the emergence of the Danish wind turbine cluster. Supplier competencies, regulations, user preferences and a market for wind power did not pre-exist; all had to emerge in a tranformative manner involving multiple actors and artefacts. Competenc......This paper employs path creation as a lens to follow the emergence of the Danish wind turbine cluster. Supplier competencies, regulations, user preferences and a market for wind power did not pre-exist; all had to emerge in a tranformative manner involving multiple actors and artefacts....... Competencies emerged through processes and mechanisms such as co-creation that implicated multiple learning processes. The process was not an orderly linear one as emergent contingencies influenced the learning processes. An implication is that public policy to catalyse clusters cannot be based...

  6. Composition of reaction intermediates for stoichiometric and fuel-rich dimethyl ether flames: flame-sampling mass spectrometry and modeling studies.

    Wang, Juan; Chaos, Marcos; Yang, Bin; Cool, Terrill A; Dryer, Fred L; Kasper, Tina; Hansen, Nils; Osswald, Patrick; Kohse-Höinghaus, Katharina; Westmoreland, Phillip R


    Molecular-beam synchrotron photoionization mass spectrometry and electron-ionization mass spectrometry are used for measurements of species mole fraction profiles for low-pressure premixed dimethyl ether (DME) flames with equivalence ratios ranging from near-stoichiometric conditions (Phi = 0.93) to fuel-rich flames near the limits of flat-flame stability (Phi = 1.86). The results are compared with predictions of a recently modified kinetic model for DME combustion [Zhao et al., Int. J. Chem. Kinet., 2008, 40, 1-18] that has been extensively tested against laminar flame speed measurements, jet-stirred reactor experiments, pyrolysis and oxidation experiments in flow reactors, species measurements for burner-stabilized flames and ignition delay measurements in shock tubes. The present comprehensive measurements of the composition of reaction intermediates over a broad range of equivalence ratios considerably extends the range of the previous experiments used for validation of this model and allows for an accurate determination of contributions of individual reactions to the formation or destruction of any given flame species. The excellent agreement between measurements and predictions found for all major and most intermediate species over the entire range of equivalence ratios provides a uniquely sensitive test of details of the kinetic model. The dependence on equivalence ratio of the characteristic reaction paths in DME flames is examined within the framework of reaction path analyses.

  7. Modeling reaction noise with a desired accuracy by using the X level approach reaction noise estimator (XARNES) method.

    Konkoli, Zoran


    A novel computational method for modeling reaction noise characteristics has been suggested. The method can be classified as a moment closure method. The approach is based on the concept of correlation forms which are used for describing spatially extended many body problems where particle numbers change in space and time. In here, it was shown how the formalism of spatially extended correlation forms can be adapted to study well mixed reaction systems. Stochastic fluctuations in particle numbers are described by selectively capturing correlation effects up to the desired order, ξ. The method is referred to as the ξ-level Approximation Reaction Noise Estimator method (XARNES). For example, the ξ=1 description is equivalent to the mean field theory (first-order effects), the ξ=2 case corresponds to the previously developed PARNES method (pair effects), etc. The main idea is that inclusion of higher order correlation effects should lead to better (more accurate) results. Several models were used to test the method, two versions of a simple complex formation model, the Michaelis-Menten model of enzymatic kinetics, the smallest bistable reaction network, a gene expression network with negative feedback, and a random large network. It was explicitly demonstrated that increase in ξ indeed improves accuracy in all cases investigated. The approach has been implemented as automatic software using the Mathematica programming language. The user only needs to input reaction rates, stoichiometry coefficients, and the desired level of computation ξ.

  8. Reaction kinetic model of the surface-mediated formation of PCDD/F from pyrolysis of 2-chlorophenol on a CuP/Silica suface

    Lomnicki, S.; Khachatryan, L.; Dellinger, B. [Louisiana State Univ., Baton Rouge (United States). Dept. of Chemistry


    One of the major challenges in developing predictive models of the surface mediated pollutant formation and fuel combustion is the construction of reliable reaction kinetic mechanisms and models. While the homogeneous, gas-phase chemistry of various light fuels such as hydrogen and methane is relatively well-known large uncertainties exist in the reaction paths of surface mediated reaction mechanisms for even these very simple species. To date, no detailed kinetic consideration of the surface mechanisms of formation of complex organics such as PCDD/F have been developed. In addition to the complexity of the mechanism, a major difficulty is the lack of reaction kinetic parameters (pre-exponential factor and activation energy) of surface reactions, Consequently, numerical studies of the surface-mediated formation of PCDD/F have often been incorporated only a few reactions. We report the development of a numerical multiple-step surface model based on experimental data of surface mediated (5% CuO/SiO2) conversion of 2-monochlorphenol (2-MCP) to PCDD/F under pyrolytic or oxidative conditions. A reaction kinetic model of the catalytic conversion of 2-MCP on the copper oxide catalyst under pyrolytic conditions was developed based on a detailed multistep surface reaction mechanism developed in our laboratory. The performance of the chemical model is assessed by comparing the numerical predictions with experimental measurements. SURFACE CHEMKIN (version 3.7.1) software was used for modeling. Our results confirm the validity of previously published mechanism of the reaction and provides new insight concerning the formation of PCDD/F formation in combustion processes. This model successfully explains the high yields of PCDD/F at low temperatures that cannot be explained using a purely gas-phase mode.

  9. Approximating Behavioral Equivalence of Models Using Top-K Policy Paths

    Zeng, Yifeng; Chen, Yingke; Prashant, Doshi


    Decision making and game play in multiagent settings must often contend with behavioral models of other agents in order to predict their actions. One approach that reduces the complexity of the unconstrained model space is to group models that tend to be behaviorally equivalent. In this paper, we...

  10. Generic Model-Based Tailor-Made Design and Analysis of Biphasic Reaction Systems

    Anantpinijwatna, Amata

    contribution of this thesis is the development of a systematic modelling framework for the biphasic reaction system. The developed framework consists of three modules describing phase equilibria, reactions and mass transfer, and material balances of such processes. Correlative and predictive thermodynamic......-elementary reaction rate laws. Extents of reaction are used to calculate the species material balances. The resulting mathematical model contains temperature dependent reaction rate parameters,equilibrium constants, and partition coefficients; where only the reaction rates are to be regressed to a minimum of time...

  11. PLS path model building: A multivariate approach to land price studies-A case study in Beijing

    Wenjie Wu; Wenzhong Zhang


    Previous studies have revealed that statistical methods can be used to analyze land-leasing parcel data. However, the conventional statistical methods used in land analysis have some limitations, especially in cases of limited observational data. In this paper, with the help of geographic information system (GIS) techniques, a partial least squares (PLS) path model is applied to study the relationship between residential land prices and various determinants through a case study of Beijing in China. From a preliminary analysis, four latent variables are selected: accessibility of the workplace center, livability, traffic, and environment facilities. The results show that the observation variables have a strong explanatory power for their corresponding latent variables, and the four latent variables have varying impacts on residential land prices. Of the latent variables, accessibility to the workplace center has the strongest impact on the residential land price.

  12. Optimal multi-agent path planning for fast inverse modeling in UAV-based flood sensing applications

    Abdelkader, Mohamed


    Floods are the most common natural disasters, causing thousands of casualties every year in the world. In particular, flash flood events are particularly deadly because of the short timescales on which they occur. Unmanned air vehicles equipped with mobile microsensors could be capable of sensing flash floods in real time, saving lives and greatly improving the efficiency of the emergency response. However, of the main issues arising with sensing floods is the difficulty of planning the path of the sensing agents in advance so as to obtain meaningful data as fast as possible. In this particle, we present a fast numerical scheme to quickly compute the trajectories of a set of UAVs in order to maximize the accuracy of model parameter estimation over a time horizon. Simulation results are presented, a preliminary testbed is briefly described, and future research directions and problems are discussed. © 2014 IEEE.

  13. A reaction diffusion model of pattern formation in clustering of adatoms on silicon surfaces

    Trilochan Bagarti


    Full Text Available We study a reaction diffusion model which describes the formation of patterns on surfaces having defects. Through this model, the primary goal is to study the growth process of Ge on Si surface. We consider a two species reaction diffusion process where the reacting species are assumed to diffuse on the two dimensional surface with first order interconversion reaction occuring at various defect sites which we call reaction centers. Two models of defects, namely a ring defect and a point defect are considered separately. As reaction centers are assumed to be strongly localized in space, the proposed reaction-diffusion model is found to be exactly solvable. We use Green's function method to study the dynamics of reaction diffusion processes. Further we explore this model through Monte Carlo (MC simulations to study the growth processes in the presence of a large number of defects. The first passage time statistics has been studied numerically.

  14. Scenario Analysis on Global Hydropower Development Paths and Their Contribution to GHG Mitigation Utilizing a Dynamic CGE Model

    Qian, Z.; Hanasaki, N.; Fujimori, S.; Masaki, Y.; Hijioka, Y.


    Currently, hydropower accounts for 16% of the worldwide electricity power supply and 86% of the total renewable electricity energy source due to its low cost, low greenhouse gas (GHG) emission, and relatively high reliability. It is well known that the global hydropower has not yet been fully developed, but the future paths of development and corresponding contribution to GHG mitigation in each region combined with socioeconomic activities are less known. Here we investigated following three questions. How much will hydropower generation increase in the future? Will hydropower generation reach the economically exploitable capability (EEC)? If this will be the case, when and where will it occur? How much GHG emission will be reduced by adding new hydropower? In order to address these questions, we used the AIM/CGE model, a dynamic computable general equilibrium model to quantify the global hydropower development paths and corresponding GHG mitigation contribution for 17 regions in the world associated with a socio-economic scenario termed SSP2. We compared two scenarios with different assumptions on EEC. One is BAU which takes EEC from the report of "World Energy Resources", the other is FIX_BAU which fix EEC at the current hydropower generation amount throughout the research period (2005-2100) or no additional installation of hydropower plants. The comparison between two scenarios indicated that promoting hydropower development contributed to GHG emission reduction globally but the magnitude varied by region. For example we found that in North Africa, hydropower development grew fast because of the rapid economic development, but it reached EEC as soon as in 2040 because of limitation in EEC due to its climatic and geographical conditions. Conversely, in Brazil, it grew steadily and did not reach its abundant EEC. Consequently, GHG mitigation contribution of North Africa is far less than Brazil. This research provides important information for policy makers to

  15. Born to Burnout: A Meta-Analytic Path Model of Personality, Job Burnout, and Work Outcomes

    Swider, Brian W.; Zimmerman, Ryan D.


    We quantitatively summarized the relationship between Five-Factor Model personality traits, job burnout dimensions (emotional exhaustion, depersonalization, and personal accomplishment), and absenteeism, turnover, and job performance. All five of the Five-Factor Model personality traits had multiple true score correlations of 0.57 with emotional…

  16. Born to Burnout: A Meta-Analytic Path Model of Personality, Job Burnout, and Work Outcomes

    Swider, Brian W.; Zimmerman, Ryan D.


    We quantitatively summarized the relationship between Five-Factor Model personality traits, job burnout dimensions (emotional exhaustion, depersonalization, and personal accomplishment), and absenteeism, turnover, and job performance. All five of the Five-Factor Model personality traits had multiple true score correlations of 0.57 with emotional…

  17. Development and Validation of a Path Analytic Model of Students' Performance in Chemistry.

    Anamuah-Mensah, Jophus; And Others


    Reported the development and validation of an integrated model of performance on chemical concept-volumetric analysis. Model was tested on 265 chemistry students in eight schools.Results indicated that for subjects using algorithms without understanding, performance on volumetric analysis problems was not influenced by proportional reasoning…

  18. Stability Analysis of a Reaction-Diffusion System Modeling Atherogenesis

    Ibragimov, Akif


    This paper presents a linear, asymptotic stability analysis for a reaction-diffusionconvection system modeling atherogenesis, the initiation of atherosclerosis, as an inflammatory instability. Motivated by the disease paradigm articulated by Ross, atherogenesis is viewed as an inflammatory spiral with a positive feedback loop involving key cellular and chemical species interacting and reacting within the intimal layer of muscular arteries. The inflammatory spiral is initiated as an instability from a healthy state which is defined to be an equilibrium state devoid of certain key inflammatory markers. Disease initiation is studied through a linear, asymptotic stability analysis of a healthy equilibrium state. Various theorems are proved, giving conditions on system parameters guaranteeing stability of the health state, and a general framework is developed for constructing perturbations from a healthy state that exhibit blow-up, which are interpreted as corresponding to disease initiation. The analysis reveals key features that arterial geometry, antioxidant levels, and the source of inflammatory components (through coupled third-kind boundary conditions or through body sources) play in disease initiation. © 2010 Society for Industrial and Applied Mathematics.

  19. A Computational Model for Path Loss in Wireless Sensor Networks in Orchard Environments

    Hristos T. Anastassiu


    Full Text Available A computational model for radio wave propagation through tree orchards is presented. Trees are modeled as collections of branches, geometrically approximated by cylinders, whose dimensions are determined on the basis of measurements in a cherry orchard. Tree canopies are modeled as dielectric spheres of appropriate size. A single row of trees was modeled by creating copies of a representative tree model positioned on top of a rectangular, lossy dielectric slab that simulated the ground. The complete scattering model, including soil and trees, enhanced by periodicity conditions corresponding to the array, was characterized via a commercial computational software tool for simulating the wave propagation by means of the Finite Element Method. The attenuation of the simulated signal was compared to measurements taken in the cherry orchard, using two ZigBee receiver-transmitter modules. Near the top of the tree canopies (at 3 m, the predicted attenuation was close to the measured one—just slightly underestimated. However, at 1.5 m the solver underestimated the measured attenuation significantly, especially when leaves were present and, as distances grew longer. This suggests that the effects of scattering from neighboring tree rows need to be incorporated into the model. However, complex geometries result in ill conditioned linear systems that affect the solver’s convergence.

  20. Modelling catchment-scale shallow landslide occurrence by means of a subsurface flow path connectivity index

    C. Lanni


    Full Text Available Topographic index-based hydrological models have gained wide use to describe the hydrological control on the triggering of rainfall-induced shallow landslides at the catchment scale. A common assumption in these models is that a spatially continuous water table occurs simultaneously at any point across the catchment. However, during a rainfall event isolated patches of subsurface saturation form above an impeding layer and hydrological connectivity of these patches is a necessary condition for lateral flow initiation at a point on the hillslope.

    Here, a new hydrological model is presented, which allows to account for the concept of hydrological connectivity while keeping the simplicity of the topographic index approach. A dynamic topographic index is used to describe the transient lateral flow that is established at a hillslope element when the rainfall amount exceeds a threshold value allowing for (a development of a perched water table above an impeding layer, (b hydrological connectivity between the hillslope element and its own upslope contributing area. A spatially variable soil depth is the main control of hydrological connectivity in the model. The hydrological model is coupled with the infinite slope stability model, and with a scaling model for the rainfall frequency-duration relationship to determine the return period of the critical rainfall needed to cause instability on three catchments located in the Italian Alps. The results show the good ability of our model in predicting observed shallow landslides. The model is finally used to determine local rainfall intensity-duration thresholds that may lead to shallow landslide initiation.

  1. Spatial separation of groundwater flow paths from a multi-flow system by a simple mixing model using stable isotopes of oxygen and hydrogen as natural tracers

    Nakaya, Shinji; Uesugi, Kenji; Motodate, Yusuke; Ohmiya, Isao; Komiya, Hiroyuki; Masuda, Harue; Kusakabe, Minoru


    Stable isotopes of oxygen and hydrogen have the potential to serve as tracers for both source and flow paths in a groundwater system. The ratios of stable isotopes of oxygen (δ18O) and hydrogen (δD) can be used as natural tracer parameters to separate multiflow groundwater paths by applying a simple inversion analysis method to determine the differences between observed and calculated δ18O and δD data in a simple mixing model. The model presented here assumes that the distribution of natural tracers in the steady state is governed by simple mixing between flow paths with a normal distribution of flow rate. When the inversion analysis and simple mixing model were applied to the multiflow system of the Matsumoto Basin, which is surrounded by Japanese alpine ranges, the end-members of the relationship between observed δ18O and δD could be separated spatially into specific groundwater flow paths in the multiflow system of shallow and deep groundwater flow paths.

  2. High-resolution mineralogical characterization and biogeochemical modeling of uranium reaction pathways at the FRC

    Chen Zhu


    High-Resolution Mineralogical Characterization and Biogeochemical Modeling of Uranium Reduction Pathways at the Oak Ridge Field-Research Center (FRC) Chen Zhu, Indiana University, David R. Veblen, Johns Hopkins University We have successfully completed a proof-of-concept, one-year grant on a three-year proposal from the former NABIR program, and here we seek additional two-year funding to complete and publish the research. Using a state-of-the-art 300-kV, atomic resolution, Field Emission Gun Transmission Electron Microscope (TEM), we have successfully identified three categories of mineral hosts for uranium in contaminated soils: (1) iron oxides; (2) mixed manganese-iron oxides; and (3) uranium phosphates. Method development using parallel electron energy loss spectroscopy (EELS) associated with the TEM shows great promise for characterizing the valence states of immobilized U during bioremediation. We have also collected 27 groundwater samples from two push-pull field biostimulation tests, which form two time series from zero to approximately 600 hours. The temporal evolution in major cations, anions, trace elements, and the stable isotopes 34S, 18O in sulfate, 15N in nitrate, and 13C in dissolved inorganic carbon (DIC) clearly show that biostimulation resulted in reduction of nitrate, Mn(IV), Fe(III), U(VI), sulfate, and Tc(VII), and these reduction reactions were intimately coupled with a complex network of inorganic reactions evident from alkalinity, pH, Na, K, Mg, and Ca concentrations. From these temporal trends, apparent zero order rates were regressed. However, our extensive suite of chemical and isotopic data sets, perhaps the first and only comprehensive data set available at the FRC, show that the derived rates from these field biostimulation experiments are composite and lump-sum rates. There were several reactions that were occurring at the same time but were masked by these pseudo-zero order rates. A reaction-path model comprising a total of nine

  3. Automatised selection of load paths to construct reduced-order models in computational damage micromechanics: from dissipation-driven random selection to Bayesian optimization

    Goury, Olivier; Amsallem, David; Bordas, Stéphane Pierre Alain; Liu, Wing Kam; Kerfriden, Pierre


    In this paper, we present new reliable model order reduction strategies for computational micromechanics. The difficulties rely mainly upon the high dimensionality of the parameter space represented by any load path applied onto the representative volume element. We take special care of the challenge of selecting an exhaustive snapshot set. This is treated by first using a random sampling of energy dissipating load paths and then in a more advanced way using Bayesian optimization associated with an interlocked division of the parameter space. Results show that we can insure the selection of an exhaustive snapshot set from which a reliable reduced-order model can be built.

  4. Dynamic voxel modeling resolution based on quality assessments from LIDAR path tracing

    Hagstrom, Shea; Broadwater, Joshua


    Airborne LIDAR instruments are capable of delivering high density point clouds, but sampling is inherently uneven in both 2D and 3D space due to collection patterns as well as effects like occlusion. Taking full advantage of the detail available when creating 3D models therefore requires that resolution be adaptable to the amount of localized data. Voxel-based modeling of LIDAR has proven advantageous in many situations, but the traditional use of a fixed grid size prevents full realization of the potential resolution. Allowing voxel sizes to vary across the model using spatial subdivision techniques overcomes this limitation. An important part of this process is defining an appropriate limit of resolution for different sections of a model, and we incorporate information gained through tracing of LIDAR pulses to guide this decision process. Real-world data are used to demonstrate our results, and we show how dynamic resolution voxelization of LIDAR allows for both reduced storage requirements as well as improved modeling flexibility.

  5. Dynamic analysis and control PID path of a model type gantry crane

    Ospina-Henao, P. A.; López-Suspes, Framsol


    This paper presents an alternate form for the dynamic modelling of a mechanical system that simulates in real life a gantry crane type, using Euler’s classical mechanics and Lagrange formalism, which allows find the equations of motion that our model describe. Moreover, it has a basic model design system using the SolidWorks software, based on the material and dimensions of the model provides some physical variables necessary for modelling. In order to verify the theoretical results obtained, a contrast was made between solutions obtained by simulation in SimMechanics-Matlab and Euler-Lagrange equations system, has been solved through Matlab libraries for solving equation’s systems of the type and order obtained. The force is determined, but not as exerted by the spring, as this will be the control variable. The objective is to bring the mass of the pendulum from one point to another with a specified distance without the oscillation from it, so that, the answer is overdamped. This article includes an analysis of PID control in which the equations of motion of Euler-Lagrange are rewritten in the state space, once there, they were implemented in Simulink to get the natural response of the system to a step input in F and then draw the desired trajectories.

  6. Gravity-dependent signal path variation in a large VLBI telescope modelled with a combination of surveying methods

    Sarti, Pierguido; Abbondanza, C.; Vittuari, L.


    The very long baseline interferometry (VLBI) antenna in Medicina (Italy) is a 32-m AZ-EL mount that was surveyed several times, adopting an indirect method, for the purpose of estimating the eccentricity vector between the co-located VLBI and Global Positioning System instruments. In order to fulfill this task, targets were located in different parts of the telescope’s structure. Triangulation and trilateration on the targets highlight a consistent amount of deformation that biases the estimate of the instrument’s reference point up to 1 cm, depending on the targets’ locations. Therefore, whenever the estimation of accurate local ties is needed, it is critical to take into consideration the action of gravity on the structure. Furthermore, deformations induced by gravity on VLBI telescopes may modify the length of the path travelled by the incoming radio signal to a non-negligible extent. As a consequence, differently from what it is usually assumed, the relative distance of the feed horn’s phase centre with respect to the elevation axis may vary, depending on the telescope’s pointing elevation. The Medicina telescope’s signal path variation Δ L increases by a magnitude of approximately 2 cm, as the pointing elevation changes from horizon to zenith; it is described by an elevation-dependent second-order polynomial function computed as, according to Clark and Thomsen (Techical report, 100696, NASA, Greenbelt, 1988), a linear combination of three terms: receiver displacement Δ R, primary reflector’s vertex displacement Δ V and focal length variations Δ F. Δ L was investigated with a combination of terrestrial triangulation and trilateration, laser scanning and a finite element model of the antenna. The antenna gain (or auto-focus curve) Δ G is routinely determined through astronomical observations. A surprisingly accurate reproduction of Δ G can be obtained with a combination of Δ V, Δ F and Δ R.

  7. They made you perfect: A test of the Social Reaction Model of Perfectionism.

    Wilson, Claire; Hunter, Simon C; Rasmussen, Susan; McGowan, Allison


    Perfectionism serves as a mediator in the relationship between difficult life experiences and psychological distress, but to date no research has examined the effect of recalled peer victimization on perfectionism and adult depressive symptomatology (DS). The present study assessed the Social Reaction Model of Perfectionism (SRMP; Flett, Hewitt, Oliver, & Macdonald (2002b). Perfectionism in children and their parents: A developmental analysis. In G. L. Flett and P. L. Hewitt (Eds.), Perfectionism: Theory, research, and treatment (pp. 89-132). Washington: American Psychological Association), which proposes that perfectionism (self-oriented, other-oriented and socially prescribed perfectionism) results from harsh experiences. This may include experiences of peer victimization (physical, verbal and indirect). The model was extended to also include adult DS and rumination (brooding and reflection). Self-report questionnaires measuring recalled childhood experiences of peer victimization (Owens, Daly, & Slee (2005). Aggressive Behavior, 31, 1-12. doi: 10.1002/ab.20045), current trait perfectionism (Hewitt & Flett (1991). Journal of Personality and Social Psychology, 60, 456-470., rumination (Nolen-Hoeksema & Morrow (1991). Journal of Personality and Social Psychology, 61, 115-121. doi: 10.1037/0022-3514.61.1.115) and DS (Radloff (1977). Applied Psychological Measurement, 1, 386-401. were completed by 338 adult participants (54% female). Path-analyses revealed recalled indirect victimization to be associated with adults' self-oriented and socially prescribed perfectionism. However, only socially prescribed perfectionism mediated the relation between recalled indirect victimization and adult DS. Brooding rumination also mediated the effect of socially prescribed perfectionism upon DS. The findings support the SRMP, and extend the theory to include the effects of perfectionism on

  8. Constructing and visualizing chemical reaction networks from pi-calculus models

    M. John; H.-J. Schulz; H. Schumann; A. M. Uhrmacher; Andrea Unger


    International audience; The pi-calculus, in particular its stochastic version the stochastic pi-calculus, is a common modeling formalism to concisely describe the chemical reactions occurring in biochemical systems. However, it remains largely unexplored how to transform a biochemical model expressed in the stochastic pi-calculus back into a set of meaningful reactions. To this end, we present a two step approach of first translating model states to reaction sets and then visualizing sequence...

  9. Modeling adsorption and reactions of organic molecules at metal surfaces.

    Liu, Wei; Tkatchenko, Alexandre; Scheffler, Matthias


    CONSPECTUS: The understanding of adsorption and reactions of (large) organic molecules at metal surfaces plays an increasingly important role in modern surface science and technology. Such hybrid inorganic/organic systems (HIOS) are relevant for many applications in catalysis, light-emitting diodes, single-molecule junctions, molecular sensors and switches, and photovoltaics. Obviously, the predictive modeling and understanding of the structure and stability of such hybrid systems is an essential prerequisite for tuning their electronic properties and functions. At present, density-functional theory (DFT) is the most promising approach to study the structure, stability, and electronic properties of complex systems, because it can be applied to both molecules and solids comprising thousands of atoms. However, state-of-the-art approximations to DFT do not provide a consistent and reliable description for HIOS, which is largely due to two issues: (i) the self-interaction of the electrons with themselves arising from the Hartree term of the total energy that is not fully compensated in approximate exchange-correlation functionals, and (ii) the lack of long-range part of the ubiquitous van der Waals (vdW) interactions. The self-interaction errors sometimes lead to incorrect description of charge transfer and electronic level alignment in HIOS, although for molecules adsorbed on metals these effects will often cancel out in total energy differences. Regarding vdW interactions, several promising vdW-inclusive DFT-based methods have been recently demonstrated to yield remarkable accuracy for intermolecular interactions in the gas phase. However, the majority of these approaches neglect the nonlocal collective electron response in the vdW energy tail, an effect that is particularly strong in condensed phases and at interfaces between different materials. Here we show that the recently developed DFT+vdW(surf) method that accurately accounts for the collective electronic

  10. Aircraft automatic digital flight control system with inversion of the model in the feed-forward path

    Smith, G. A.; Meyer, G.


    A full-flight-envelope automatic trajectory control system concept is being investigated at Ames Research Center. This concept was developed for advanced aircraft configurations with severe nonlinear characteristics. A feature of the system is an inverse of the complete nonlinear aircraft model as part of the feed-forward control path. Simulation and flight tests have been reported at previous Digital Avionics Systems conferences. A new method for the continuous real-time inversion of the aircraft model using a Newton-Raphson trim algorithm instead of the original inverse table look-up procedure has been developed. The results of a simulation study of a vertical attitude takeoff and landing aircraft using the new inversion technique are presented. Maneuvers were successfully carried out in all directions in the vertical-attitude hover mode. Transition runs from conventional flight through the region of lift-curve-slope reversal at an angle of attack of about 32 deg and to hover at zero speed in the vertical attitude showed satisfactory transient response. Simulations were also conducted in conventional flight at high subsonic speed in steep climb and with turns up to 4 g. Successful flight tests of the system with the new model-inversion technique in a UH-1H helicopter have recently been carried out.

  11. Off The Beaten Path: Modeling the Dynamics of Supermassive Black Holes in Cosmological Simulations

    Tremmel, Michael J.; Governato, Fabio; Volonteri, Marta; Quinn, Thomas R.


    Cosmological simulations are an essential tool to understand the co-evolution of supermassive black holes (SMBHs) and their host galaxies. However, the limited resolution of these simulations presents unique challenges to successfully modeling black hole dynamics. We present a novel, physically motivated method for improving the dynamics of black holes in cosmological simulations, by accounting for the unresolved dynamical friction that SMBHs feel from stars and dark matter. We show how this approach, which naturally scales with resolution, is a major step forward compared to more commonly used 'advection' models that often assume SMBHs sink very rapidly toward the center of their host galaxies. Here, we demonstrate that our method is able to prevent numerical heating of SMBHs while allowing for realistic dynamics.Our implementation will allow us to more realistically model SMBH dynamics, accretion, and mergers in cosmological simulations, giving us the ability to better understand how SMBHs grow with their host galaxies. This also provides an opportunity for more detailed studies of SMBHs in dwarf galaxies, which can give crucial insight into constraining black hole seed formation models.

  12. The Path to Graduation: A Model Interactive Web Site Design Supporting Doctoral Students

    Simmons-Johnson, Nicole


    Objective. This 2-phase mixed method study assessed 2nd-year doctoral students' and dissertation students' perceptions of the current Graduate School of Education dissertation support Web site, with implications for designing a model dissertation support Web site. Methods. Phase 1 collected quantitative and qualitative data through an…

  13. A Path Loss Model for Non-Line-of-Sight Ultraviolet Multiple Scattering Channels


    relevant model parameters. 2.3. Elementary Events for Photon RandomMigration. Gener- ally, it is impossible to predict with certainty the trajectory of a...Witt, “Multiple scattering in reflection nebulae—I: a Monte Carlo approach,” The Astrophysical Journal Supplement Series, vol. 35, pp. 1–6, 1977. [22] D

  14. The Path to Graduation: A Model Interactive Web Site Design Supporting Doctoral Students

    Simmons-Johnson, Nicole


    Objective. This 2-phase mixed method study assessed 2nd-year doctoral students' and dissertation students' perceptions of the current Graduate School of Education dissertation support Web site, with implications for designing a model dissertation support Web site. Methods. Phase 1 collected quantitative and qualitative data through an…

  15. Career Indecision, Anxiety, and Social Problem Solving: A Path Analytic Model.

    Gribben, Carolyn A.; Keitel, Merle A.

    While previous studies have correlated career indecision with state and trait anxiety in college students, most researchers have examined the relationship between anxiety and career indecision without considering other variables. This paper, incorporating previous research on career indecision, profiles a study of a causal model of career…

  16. Statistical Modeling of Large-Scale Signal Path Loss in Underwater Acoustic Networks

    Manuel Perez Malumbres


    Full Text Available In an underwater acoustic channel, the propagation conditions are known to vary in time, causing the deviation of the received signal strength from the nominal value predicted by a deterministic propagation model. To facilitate a large-scale system design in such conditions (e.g., power allocation, we have developed a statistical propagation model in which the transmission loss is treated as a random variable. By applying repetitive computation to the acoustic field, using ray tracing for a set of varying environmental conditions (surface height, wave activity, small node displacements around nominal locations, etc., an ensemble of transmission losses is compiled and later used to infer the statistical model parameters. A reasonable agreement is found with log-normal distribution, whose mean obeys a log-distance increases, and whose variance appears to be constant for a certain range of inter-node distances in a given deployment location. The statistical model is deemed useful for higher-level system planning, where simulation is needed to assess the performance of candidate network protocols under various resource allocation policies, i.e., to determine the transmit power and bandwidth allocation necessary to achieve a desired level of performance (connectivity, throughput, reliability, etc..

  17. Empirical valence bond model of an SN2 reaction in polar and nonpolar solvents

    Benjamin, Ilan


    A new model for the substitution nucleophilic reaction (SN2) in solution is described using the empirical valence bond (EVB) method. The model includes a generalization to three dimensions of a collinear gas phase EVB model developed by Mathis et al. [J. Mol. Liq. 61, 81 (1994)] and a parametrization of solute-solvent interactions of four different solvents (water, ethanol, chloroform, and carbon tetrachloride). The model is used to compute (in these four solvents) reaction free energy profiles, reaction and solvent dynamics, a two-dimensional reaction/solvent free energy map, as well as a number of other properties that in the past have mostly been estimated.

  18. Modelling of reaction cross sections and prompt neutron emission

    Hambsch, F.-J.; Tudora, A.; Oberstedt, S.


    Accurate nuclear data concerning reaction cross sections and the emission of prompt fission neutrons (i.e. multiplicity and spectra) as well as other fission fragment data are of great importance for reactor physics design, especially for the new Generation IV nuclear energy systems. During the past years for several actinides (238U(n, f) and 237Np(n, f)) both the reaction cross sections and prompt neutron multiplicities and spectra have been calculated within the frame of the EFNUDAT project.

  19. Comparison of a Reaction Front Model and a Finite Difference Model for the Simulation of Solid Absorption Process

    ZikangWu; ArneJakobsen; 等


    The pupose of this paper is to investigate the validity of a lumped model,i.e.a reaction front model,for the simulation of solid absorption process.A distributed model is developed for solid absorption process,and a dimensionless RF number is suggested to predict the qualitative shape of reaction degree profile.The simulation results from the reaction front model are compared with those from the distributed model solved by a finite difference scheme,and it is shown that they are in good agreement in almost all matter whether there is reaction front or not.

  20. A general paradigm to model reaction-based biogeochemical processes in batch systems

    Fang, Yilin; Yeh, Gour-Tsyh; Burgos, William D.


    This paper presents the development and illustration of a numerical model of reaction-based geochemical and biochemical processes with mixed equilibrium and kinetic reactions. The objective is to provide a general paradigm for modeling reactive chemicals in batch systems, with expectations that it is applicable to reactive chemical transport problems. The unique aspects of the paradigm are to simultaneously (1) facilitate the segregation (isolation) of linearly independent kinetic reactions and thus enable the formulation and parameterization of individual rates one reaction by one reaction when linearly dependent kinetic reactions are absent, (2) enable the inclusion of virtually any type of equilibrium expressions and kinetic rates users want to specify, (3) reduce problem stiffness by eliminating all fast reactions from the set of ordinary differential equations governing the evolution of kinetic variables, (4) perform systematic operations to remove redundant fast reactions and irrelevant kinetic reactions, (5) systematically define chemical components and explicitly enforce mass conservation, (6) accomplish automation in decoupling fast reactions from slow reactions, and (7) increase the robustness of numerical integration of the governing equations with species switching schemes. None of the existing models to our knowledge has included these scopes simultaneously. This model (BIOGEOCHEM) is a general computer code to simulate biogeochemical processes in batch systems from a reaction-based mechanistic standpoint, and is designed to be easily coupled with transport models. To make the model applicable to a wide range of problems, programmed reaction types include aqueous complexation, adsorption-desorption, ion-exchange, oxidation-reduction, precipitation-dissolution, acid-base reactions, and microbial mediated reactions. In addition, user-specified reaction types can be programmed into the model. Any reaction can be treated as fast/equilibrium or slow

  1. Chemical reaction networks as a model to describe UVC- and radiolytically-induced reactions of simple compounds.

    Dondi, Daniele; Merli, Daniele; Albini, Angelo; Zeffiro, Alberto; Serpone, Nick


    When a chemical system is submitted to high energy sources (UV, ionizing radiation, plasma sparks, etc.), as is expected to be the case of prebiotic chemistry studies, a plethora of reactive intermediates could form. If oxygen is present in excess, carbon dioxide and water are the major products. More interesting is the case of reducing conditions where synthetic pathways are also possible. This article examines the theoretical modeling of such systems with random-generated chemical networks. Four types of random-generated chemical networks were considered that originated from a combination of two connection topologies (viz., Poisson and scale-free) with reversible and irreversible chemical reactions. The results were analyzed taking into account the number of the most abundant products required for reaching 50% of the total number of moles of compounds at equilibrium, as this may be related to an actual problem of complex mixture analysis. The model accounts for multi-component reaction systems with no a priori knowledge of reacting species and the intermediates involved if system components are sufficiently interconnected. The approach taken is relevant to an earlier study on reactions that may have occurred in prebiotic systems where only a few compounds were detected. A validation of the model was attained on the basis of results of UVC and radiolytic reactions of prebiotic mixtures of low molecular weight compounds likely present on the primeval Earth.

  2. Path modelling of antecedent of diabetes mellitus on blood glucose measurements

    Latif, Humaira'Abdul; Hamid, Mohd Rashid Ab; Azizan, Nor Azlinna; Jemain, Abdul Aziz


    Diabetes Mellitus (DM) is one of the non-communicable diseases and public health problems facing the worldwide population that includes Malaysia. Hitherto, the prevalence of DM becomes worsening with an estimated of 3.4 million Malaysians are diabetes sufferers and expectedly increasing year by year. Thus, this study is of great importance by regressing the medical factors that affect the blood glucose level using structural equation modelling (SEM). The SEM with partial least squares (PLS) estimation was applied to a secondary data of 644 respondents, aged ≥ 18 years in Malaysia. The data were collected in 2011 by Ministry of Health Malaysia (MOH). The variables under study are blood glucose level, cholesterol level (CL), systolic blood pressure (SBP), diastolic blood pressure (DBP), waist circumference (WC) and body mass index (BMI). From the modelling analysis, it showed that the cholesterol level (CL), systolic blood pressure (SBP) and waist circumference (WC) showed a positive significant relationship p diabetes mellitus among adults.

  3. The Derivation and Use of a Scalable Model for Network Attack Identification and Path Prediction

    Sanjeeb Nanda


    Full Text Available The rapid growth of the Internet has triggered an explosion in the number of applications that leverage its capabilities. Unfortunately, many are designed to burden or destroy the capabilities of their peers and the network's infrastructure. Hence, considerable effort has been focused on detecting and predicting the security breaches they propagate. However, the enormity of the Internet poses a formidable challenge to analyzing such attacks using scalable models. Furthermore, the lack of complete information on network vulnerabilities makes forecasting the systems that may be exploited by such applications in the future very hard. This paper presents a technique for deriving a scalable model for representing network attacks, and its application to identify actual attacks with greater certainty amongst false positives and false negatives. It also presents a method to forecast the propagation of security failures proliferated by an attack over time and its likely targets in the future.


    Carlos Monge Perry


    Full Text Available Structural equation modeling (SEM has traditionally been deployed in areas of marketing, consumer satisfaction and preferences, human behavior, and recently in strategic planning. These areas are considered their niches; however, there is a remarkable tendency in empirical research studies that indicate a more diversified use of the technique.  This paper shows the application of structural equation modeling using partial least square (PLS-SEM, in areas of manufacturing, quality, continuous improvement, operational efficiency, and environmental responsibility in Mexico’s medium and large manufacturing plants, while using a small sample (n = 40.  The results obtained from the PLS-SEM model application mentioned, are highly positive, relevant, and statistically significant. Also shown in this paper, for purposes of validity, reliability, and statistical power confirmation of PLS-SEM, is a comparative analysis against multiple regression showing very similar results to those obtained by PLS-SEM.  This fact validates the use of PLS-SEM in areas of untraditional scientific research, and suggests and invites the use of the technique in diversified fields of the scientific research

  5. A reaction-based river/stream water quality model: Model development and numerical schemes

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C.; Jardine, Philip M.


    SummaryThis paper presents the conceptual and mathematical development of a numerical model of sediment and reactive chemical transport in rivers and streams. The distribution of mobile suspended sediments and immobile bed sediments is controlled by hydrologic transport as well as erosion and deposition processes. The fate and transport of water quality constituents involving a variety of chemical and physical processes is mathematically described by a system of reaction equations for immobile constituents and advective-dispersive-reactive transport equations for mobile constituents. To circumvent stiffness associated with equilibrium reactions, matrix decomposition is performed via Gauss-Jordan column reduction. After matrix decomposition, the system of water quality constituent reactive transport equations is transformed into a set of thermodynamic equations representing equilibrium reactions and a set of transport equations involving no equilibrium reactions. The decoupling of equilibrium and kinetic reactions enables robust numerical integration of the partial differential equations (PDEs) for non-equilibrium-variables. Solving non-equilibrium-variable transport equations instead of individual water quality constituent transport equations also reduces the number of PDEs. A variety of numerical methods are investigated for solving the mixed differential and algebraic equations. Two verification examples are compared with analytical solutions to demonstrate the correctness of the code and to illustrate the importance of employing application-dependent numerical methods to solve specific problems.

  6. Theoretical reaction rates of the $^{12}$C($\\alpha$,$\\gamma$)$^{16}$O reaction from the potential model

    Katsuma, M


    The radiative capture cross sections of $^{12}$C($\\alpha$,$\\gamma$)$^{16}$O and derived reaction rates are calculated from the direct capture potential model. The resulting $S$-factor at low energies is found to be dominated by $E$2 transition to the $^{16}$O ground state. The $E$1 and $E$2 $S$-factors at $E_{c.m.}=0.3$ MeV are $S_{E1}\\approx3$ keV~b and $S_{E2}=150^{+41}_{-17}$ keV~b, respectively. The sum of the cascade transition through the excited state of $^{16}$O is $S_{\\rm casc}= 18\\pm4.5$ keV~b. The derived reaction rates at low temperatures seem to be concordant with those from the previous evaluation. For astrophysical applications, our reaction rates below $T_9=3$ are provided in an analytic expression.

  7. Aircraft automatic-flight-control system with inversion of the model in the feed-forward path using a Newton-Raphson technique for the inversion

    Smith, G. A.; Meyer, G.; Nordstrom, M.


    A new automatic flight control system concept suitable for aircraft with highly nonlinear aerodynamic and propulsion characteristics and which must operate over a wide flight envelope was investigated. This exact model follower inverts a complete nonlinear model of the aircraft as part of the feed-forward path. The inversion is accomplished by a Newton-Raphson trim of the model at each digital computer cycle time of 0.05 seconds. The combination of the inverse model and the actual aircraft in the feed-forward path alloys the translational and rotational regulators in the feedback path to be easily designed by linear methods. An explanation of the model inversion procedure is presented. An extensive set of simulation data for essentially the full flight envelope for a vertical attitude takeoff and landing aircraft (VATOL) is presented. These data demonstrate the successful, smooth, and precise control that can be achieved with this concept. The trajectory includes conventional flight from 200 to 900 ft/sec with path accelerations and decelerations, altitude changes of over 6000 ft and 2g and 3g turns. Vertical attitude maneuvering as a tail sitter along all axes is demonstrated. A transition trajectory from 200 ft/sec in conventional flight to stationary hover in the vertical attitude includes satisfactory operation through lift-cure slope reversal as attitude goes from horizontal to vertical at constant altitude. A vertical attitude takeoff from stationary hover to conventional flight is also demonstrated.

  8. The paths leading from attachment to ageism: a structural equation model approach.

    Bodner, Ehud; Cohen-Fridel, Sara


    The study introduces a model in which attachment patterns serve as predictors, empathy and fear of death as mediators, and ageism as the predicted variable. Data were collected from young adults (N = 440). Anxious attachment was directly and positively correlated with ageism, and also indirectly and positively by the mediator "fear of death." Avoidant attachment was indirectly and negatively correlated with ageism by the mediator "empathy". It is suggested that interventions for reducing ageist attitudes among younger adults would focus on existential fears, as well as on empathic ability, according to the attachment tendencies of these individuals.

  9. Fault Tree Model for Failure Path Prediction of Bolted Steel Tension Member in a Structural System

    Biswajit Som


    Full Text Available Fault tree is a graphical representation of various sequential combinations of events which leads to the failure of any system, such as a structural system. In this paper it is shown that a fault tree model is also applicable to a critical element of a complex structural system. This will help to identify the different failure mode of a particular structural element which might eventually triggered a progressive collapse of the whole structural system. Non-redundant tension member generally regarded as a Fracture Critical Member (FCM in a complex structural system, especially in bridge, failure of which may lead to immediate collapse of the structure. Limit state design is governed by the failure behavior of a structural element at its ultimate state. Globally, condition assessment of an existing structural system, particularly for bridges, Fracture Critical Inspection becomes very effective and mandatory in some countries. Fault tree model of tension member, presented in this paper can be conveniently used to identify the flaws in FCM if any, in an existing structural system and also as a check list for new design of tension member.


    LIU An-guo; YANG Kai-zhong


    This paper meant to analyze the spatial evolution of a large country in its process of integration with the world economy in general, and, to look into the possible effect of China's accession into WTO on the future development of its spatial economy in particular. Through an approach of increasing returns, external economy, product differentiation and path-dependence, with foreign trade costs incurred by different regions within the large country discriminated, a model of investment and employment flow is developed as a simulation of a large country's process of integration with the world economy. The modeling indicates that in the process of integration, as there exist differences in foreign trade costs among different regions within the large country, either the spatial economy of the country deviates from its symmetric structure in autarky and falls into a core-periphery relationship, or the effect of industrial agglomeration is reinforced, amplified and locked in, if the agglomeration had been started. The economic gap on either the aggregate or structural basis between different regions within the large country will increase rapidly as the integration proceeds.

  11. Quantum dynamics in the highly discrete, commensurate Frenkel Kontorova model: A path-integral molecular dynamics study

    Krajewski, Florian R.; Müser, Martin H.


    The commensurate Frenkel Kontorova (FK) model is studied using path-integral molecular dynamics (PIMD). We focus on the highly discrete case, in which the embedding potential has a much greater maximum curvature than the harmonic potential connecting two particles in the FK chain. When efficient sampling methods are used, the dynamical interpretation of adiabatic PIMD appears to represent quite accurately the true time correlation functions of this highly correlated many-body system. We have found that the discrete, quantum FK model shows different behavior than its continuum version. The spectral density does not show the characteristic ω-2Θ(ω-ωc) cusp of the continuum solution in the pinned phase (m>mc). We also identify a dynamical quantum hysteresis in addition to the regular classical hysteresis when an external force is applied to the FK chain. In the unpinned phase (m⩽mc), we find a linear response damping coefficient which is finite and only weakly dependent on temperature T at small values of T.

  12. MARMOSET: The Path from LHC Data to the New Standard Model via On-Shell Effective Theories

    Arkani-Hamed, Nima; Schuster, Philip; Toro, Natalia; /Harvard U., Phys. Dept.; Thaler, Jesse; /UC, Berkeley /LBL, Berkeley; Wang, Lian-Tao; /Princeton U.; Knuteson, Bruce; /MIT, LNS; Mrenna, Stephen; /Fermilab


    We describe a coherent strategy and set of tools for reconstructing the fundamental theory of the TeV scale from LHC data. We show that On-Shell Effective Theories (OSETs) effectively characterize hadron collider data in terms of masses, production cross sections, and decay modes of candidate new particles. An OSET description of the data strongly constrains the underlying new physics, and sharply motivates the construction of its Lagrangian. Simulating OSETs allows efficient analysis of new-physics signals, especially when they arise from complicated production and decay topologies. To this end, we present MARMOSET, a Monte Carlo tool for simulating the OSET version of essentially any new-physics model. MARMOSET enables rapid testing of theoretical hypotheses suggested by both data and model-building intuition, which together chart a path to the underlying theory. We illustrate this process by working through a number of data challenges, where the most important features of TeV-scale physics are reconstructed with as little as 5 fb{sup -1} of simulated LHC signals.

  13. A morphological adaptation approach to path planning inspired by slime mould

    Jones, Jeff


    Path planning is a classic problem in computer science and robotics which has recently been implemented in unconventional computing substrates such as chemical reaction-diffusion computers. These novel computing schemes utilise the parallel spatial propagation of information and often use a two-stage method involving diffusive propagation to discover all paths and a second stage to highlight or visualise the path between two particular points in the arena. The true slime mould Physarum polycephalum is known to construct efficient transport networks between nutrients in its environment. These networks are continuously remodelled as the organism adapts its body plan to changing spatial stimuli. It can be guided towards attractant stimuli (nutrients, warm regions) and it avoids locations containing hazardous stimuli (light irradiation, repellents, or regions occupied by predatory threats). Using a particle model of slime mould we demonstrate scoping experiments which explore how path planning may be performed by morphological adaptation. We initially demonstrate simple path planning by a shrinking blob of virtual plasmodium between two attractant sources within a polygonal arena. We examine the case where multiple paths are required and the subsequent selection of a single path from multiple options. Collision-free paths are implemented via repulsion from the borders of the arena. Finally, obstacle avoidance is implemented by repulsion from obstacles as they are uncovered by the shrinking blob. These examples show proof-of-concept results of path planning by morphological adaptation which complement existing research on path planning in novel computing substrates.

  14. Optimal paths as correlated random walks

    Perlsman, E.; Havlin, S.


    A numerical study of optimal paths in the directed polymer model shows that the paths are similar to correlated random walks. It is shown that when a directed optimal path of length t is divided into 3 segments whose length is t/3, the correlation between the transversal movements along the first and last path segments is independent of the path length t. It is also shown that the transversal correlations along optimal paths decrease as the paths approach their endpoints. The numerical results obtained for optimal paths in 1+4 dimensions are qualitatively similar to those obtained for optimal paths in lower dimensions, and the data supplies a strong numerical indication that 1+4 is not the upper critical dimension of this model, and of the associated KPZ equation.

  15. Satellite Observations and Chemistry Climate Models - A Meandering Path Towards Better Predictions

    Douglass, Anne R.


    Knowledge of the chemical and dynamical processes that control the stratospheric ozone layer has grown rapidly since the 1970s, when ideas that depletion of the ozone layer due to human activity were put forth. The concept of ozone depletion due to anthropogenic chlorine increase is simple; quantification of the effect is much more difficult. The future of stratospheric ozone is complicated because ozone is expected to increase for two reasons: the slow decrease in anthropogenic chlorine due to the Montreal Protocol and its amendments and stratospheric cooling caused by increases in carbon dioxide and other greenhouse gases. Prediction of future ozone levels requires three-dimensional models that represent physical, photochemical and radiative processes, i.e., chemistry climate models (CCMs). While laboratory kinetic and photochemical data are necessary inputs for a CCM, atmospheric measurements are needed both to reveal physical and chemical processes and for comparison with simulations to test the conceptual model that CCMs represent. Global measurements are available from various satellites including but not limited to the LIMS and TOMS instruments on Nimbus 7 (1979 - 1993), and various instruments on the Upper Atmosphere Research Satellite (1991 - 2005), Envisat (2002 - ongoing), Sci-Sat (2003 - ongoing) and Aura (2004 - ongoing). Every successful satellite instrument requires a physical concept for the measurement, knowledge of physical chemical properties of the molecules to be measured, and stellar engineering to design an instrument that will survive launch and operate for years with no opportunity for repair but providing enough information that trend information can be separated from any instrument change. The on-going challenge is to use observations to decrease uncertainty in prediction. This talk will focus on two applications. The first considers transport diagnostics and implications for prediction of the eventual demise of the Antarctic ozone hole

  16. Graphical representation of life paths to better convey results of decision models to patients.

    Rubrichi, Stefania; Rognoni, Carla; Sacchi, Lucia; Parimbelli, Enea; Napolitano, Carlo; Mazzanti, Andrea; Quaglini, Silvana


    The inclusion of patients' perspectives in clinical practice has become an important matter for health professionals, in view of the increasing attention to patient-centered care. In this regard, this report illustrates a method for developing a visual aid that supports the physician in the process of informing patients about a critical decisional problem. In particular, we focused on interpretation of the results of decision trees embedding Markov models implemented with the commercial tool TreeAge Pro. Starting from patient-level simulations and exploiting some advanced functionalities of TreeAge Pro, we combined results to produce a novel graphical output that represents the distributions of outcomes over the lifetime for the different decision options, thus becoming a more informative decision support in a context of shared decision making. The training example used to illustrate the method is a decision tree for thromboembolism risk prevention in patients with nonvalvular atrial fibrillation.

  17. Research Spotlight: Model suggests path to ending the ongoing Haitian cholera epidemic

    Schultz, Colin


    Since early November 2010 a deadly cholera epidemic has been spreading across the Caribbean nation of Haiti, killing thousands of people and infecting hundreds of thousands. While infection rates are being actively monitored, health organizations have been left without a clear understanding of exactly how the disease has spread across Haiti. Cholera can spread through exposure to contaminated water, and the disease travels over long distances if an infected individual moves around the country. Using representations of these two predominant dispersion mechanisms, along with information on the size of the susceptible population, the number of infected individuals, and the aquatic concentration of the cholera-causing bacteria for more than 500 communities, Bertuzzo et al. designed a model that was able to accurately reproduce the progression of the Haitian cholera epidemic. (Geophysical Research Letters, doi:10.1029/2011GL046823, 2011)

  18. Openness to Experience and Night-Sky Watching Interest as Predictors of Reading for Pleasure: Path Analysis of a Mediation Model

    Kelly, William E.


    The relation between reading for pleasure, night-sky watching interest, and openness to experience were examined in a sample of 129 college students. Results of a path analysis examining a mediation model indicated that the influence of night-sky interest on reading for pleasure was not mediated by the broad personality domain openness to…

  19. The Health Action Process Approach as a Motivational Model of Dietary Self-Management for People with Multiple Sclerosis: A Path Analysis

    Chiu, Chung-Yi; Lynch, Ruth Torkelson; Chan, Fong; Rose, Lindsey


    The main objective of this study was to evaluate the health action process approach (HAPA) as a motivational model for dietary self-management for people with multiple sclerosis (MS). Quantitative descriptive research design using path analysis was used. Participants were 209 individuals with MS recruited from the National MS Society and a…

  20. Modelling of reaction cross sections and prompt neutron emission

    Oberstedt S.


    Full Text Available Accurate nuclear data concerning reaction cross sections and the emission of prompt fission neutrons (i.e. multiplicity and spectra as well as other fission fragment data are of great importance for reactor physics design, especially for the new Generation IV nuclear energy systems. During the past years for several actinides (238U(n, f and 237Np(n, f both the reaction cross sections and prompt neutron multiplicities and spectra have been calculated within the frame of the EFNUDAT project.