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At least 541 records · Page 30

Fine-tuning catalytic selectivity by modulating catalyst-environment interactions: CO 2 hydrogenation over Pd-based catalysts

Capturing catalytic behaviors under operational conditions is pivotal to gaining a mechanistic understanding and promoting the design of robust catalysts. The challenge lies in the difficulty of monitoring real-time surface dynamics driven by catalyst-environment interactions. Here, in this work, we introduce a framework based on density functional calculations and kinetic modeling. This framework significantly improves the accuracy of theoretical models’ descriptions of experimental observations by quantifying environmental impacts on surface phases and active sites. CO 2 hydrogenation over Pd-based catalysts is taken as a showcase. The observed selectivity variations of Pd and Pd-M bimetallic catalysts strongly correlate with hydrogen coverage maintained under typical CO 2 hydrogenation conditions. By reducing the amount of surface hydrogen, the selectivity tuned effectively from formic acid toward CO and methanol. This study not only deepens the comprehension of dynamics of active sites under active chemical conditions but also introduces an alternative opportunity for catalytic tuning by modulating catalyst-environment interactions.

03 NATURAL GAS↗

Kinetics of solid–liquid interface motion in molecular dynamics and phase-field models: crystallization of chromium and silicon

The results of molecular dynamics (MD) simulations of the crystallization process in one-component materials and solid solution alloys reveal a complex temperature dependence of the velocity of the crystal–liquid interface featuring an increase up to a maximum at 10–30% undercooling below the equilibrium melting temperature followed by a gradual decrease of the velocity at deeper levels of undercooling. At the qualitative level, such non-monotonous behaviour of the crystallization front velocity is consistent with the diffusion-controlled crystallization process described by the Wilson–Frenkel model, where the almost linear increase of the interface velocity in the vicinity of melting temperature is defined by the growth of the thermodynamic driving force for the phase transformation, while the decrease in atomic mobility with further increase of the undercooling drives the velocity through the maximum and into a gradual decrease at lower temperatures. At the quantitative level, however, the diffusional model fails to describe the results of MD simulations in the whole range of temperatures with a single set of parameters for some of the model materials. The limited ability of the existing theoretical models to adequately describe the MD results is illustrated in the present work for two materials, chromium and silicon. It is also demonstrated that the MD results can be well described by the solution following from the hodograph equation, previously found from the kinetic phase-field model (kinetic PFM) in the sharp interface limit. The ability of the hodograph equation to describe the predictions of MD simulation in the whole range of temperatures is related to the introduction of slow (phase field) and fast (gradient flow) variables into the original kinetic PFM from which the hodograph equation is obtained. The slow phase-field variable is responsible for the description of data at small undercoolings and the fast gradient flow variable accounts for local non-equilibrium effects at high undercoolings. The introduction of these two types of variables makes the solution of the hodograph equation sufficiently flexible for a reliable description of all nonlinearities of the kinetic curves predicted in MD simulations of Cr and Si. This article is part of the theme issue ‘Transport phenomena in complex systems (part 1)’.

Science & Technology - Other Topics↗

Prehydrodynamic evolution and its impact on quark-gluon plasma signatures

State-of-the-art hydrodynamic models of heavy-ion collisions have considerable theoretical model uncertainties in the description of the very early prehydrodynamic stage. Here we add a new computational module, K T Iso, that describes the prehydrodynamic evolution kinetically, based on the relativistic Boltzmann equation with collisions treated in the isotropization time approximation. As a novelty, K T Iso allows for the inclusion and evolution of initial-state momentum anisotropies. To maintain computational efficiency K T Iso assumes strict longitudinal boost invariance and allows collisions to isotropize only the transverse momenta. We use it to explore the sensitivity of hadronic observables measured in relativistic heavy-ion collisions to initial-state momentum anisotropies and microscopic scattering during the prehydrodynamic stage.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Asymmetric emission-line regions with out-flowing mass in QSOs and the z/ab/ at least equal to z/em/ systems

A heuristic asymmetrical model for a quasar emission-line region, with material streaming out, is described. The physical parameters are essentially the same as those of static models; the geometry turns out to be the dominant factor in determining the emission line profiles. Calculations are carried out for a variety of parameterized flow models and for the Blumenthal and Mathews (1975) theoretical model of a radiatively driven flow. The emission-line profiles are insensitive to the details of the acceleration, the filling factor, and the ionization profile. Absorption is assumed to take place in stationary matter in the QSO's galaxy or associated group or cluster, so that z(ab) is identified with the cosmological redshift. Due to the flow, the emission-lines are shifted with respect to the absorption-lines; in cases of a flow directed towards the observer systems with z(ab) at least equal to z(em) result. The distribution of absorption redshifts is symmetric about z(em).

Goldman, I.↗

Resource utilization model for the algorithm to architecture mapping model

The analytical model for resource utilization and the variable node time and conditional node model for the enhanced ATAMM model for a real-time data flow architecture are presented in this research. The Algorithm To Architecture Mapping Model, ATAMM, is a Petri net based graph theoretic model developed at Old Dominion University, and is capable of modeling the execution of large-grained algorithms on a real-time data flow architecture. Using the resource utilization model, the resource envelope may be obtained directly from a given graph and, consequently, the maximum number of required resources may be evaluated. The node timing diagram for one iteration period may be obtained using the analytical resource envelope. The variable node time model, which describes the change in resource requirement for the execution of an algorithm under node time variation, is useful to expand the applicability of the ATAMM model to heterogeneous architectures. The model also describes a method of detecting the presence of resource limited mode and its subsequent prevention. Graphs with conditional nodes are shown to be reduced to equivalent graphs with time varying nodes and, subsequently, may be analyzed using the variable node time model to determine resource requirements. Case studies are performed on three graphs for the illustration of applicability of the analytical theories.

Stoughton, John W.↗

Exploration of Heat-Driven Ejector High-Temperature Heat Pumps

Heat-driven ejector heat pumps use a supersonic ejector as a thermo-compressor to replace the mechanical compressor. Supersonic ejectors have many advantages in high-temperature heat pump (HTHP) applications, including high operating temperature tolerance, no need for lubrication, low maintenance, and low cost. The coefficient of performance of ejector HTHPs could be improved by selecting binary fluids with unique thermodynamic properties. Although supersonic ejectors have been widely used in refrigeration systems, their application in spaces and water heating is limited. This study explores the theoretical potential of ejector HTHPs with a sink temperature of 100°C–130°C and a lift temperature of 10°C–30°C. Ejector HTHPs were evaluated with single-fluid ejectors (SFEs) and binary-fluid ejectors (BFEs). A comprehensive, geometry-free theoretical model of BFEs was developed to predict the theoretical maximum entrainment ratios. HFE7500 and R718 (water) were selected as working fluids for SFEs and BFEs. SFEs operating with R718 provided a higher coefficient of performance of ejector HTHPs than SFEs operating with HFE7500 and BFEs. This study preliminarily demonstrates the technical potential of ejector HTHP applications in recovering moderate-temperature heat sources

Wang, Pengtao↗

Thermalization from quantum entanglement: Jet simulations in the massive Schwinger model

We investigate the emergence of thermalization in a quantum-field-theoretic model mimicking the production of jets in QCD: the massive lattice Schwinger model coupled to external sources. Specifically, we compute the expectation values of local operators as functions of time and compare them to their thermal counterparts, quantify the overlap between the evolving density matrix and the thermal one, and compare the dynamics of the energy-momentum tensor to predictions from relativistic hydrodynamics. Through these studies, we find that the system approaches thermalization at late times and elucidate the mechanisms by which quantum entanglement drives thermalization in closed field-theoretic systems. Our results show how thermodynamic behavior emerges in real time from unitary quantum dynamics.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Graph-Based Modeling and Decomposition of Hierarchical Optimization Problems

We present a graph-theoretic modeling approach for hierarchical optimization that leverages the OptiGraph abstraction implemented in the Julia package Plasmo.jl. We show that the abstraction is flexible and can effectively capture complex hierarchical connectivity that arises from decision-making over multiple spatial and temporal scales (e.g., integration of planning, scheduling, and operations in manufacturing and infrastructures). We also show that the graph abstraction facilitates the conceptualization and implementation of decomposition and approximation schemes. Specifically, we propose a graph-based Benders decomposition (gBD) framework that enables the exploitation of hierarchical (nested) structures and that uses graph aggregation/partitioning procedures to discover such structures. In addition, we provide a Julia implementation of gBD, which we call PlasmoBenders.jl. We illustrate the capabilities using examples arising in the context of energy and power systems.

97 MATHEMATICS AND COMPUTING↗

A model-based analysis of a display for helicopter landing approach

A control theoretic model of the human pilot was used to analyze a baseline electronic cockpit display in a helicopter landing approach task. The head down display was created on a stroke written cathode ray tube and the vehicle was a UH-1H helicopter. The landing approach task consisted of maintaining prescribed groundspeed and glideslope in the presence of random vertical and horizontal turbulence. The pilot model was also used to generate and evaluate display quickening laws designed to improve pilot vehicle performance. A simple fixed base simulation provided comparative tracking data.

Hess, R. A.↗

A model-based analysis of a display for helicopter landing approach

A control theoretic model of the human pilot was used to analyze a baseline electronic cockpit display in a helicopter landing approach task and to generate display quickening laws designed to improve pilot-vehicle performance. A simple fixed base simulation provided comparative tracking data which allowed refinement of the pilot model.

Hess, R. A.↗

Modeling of gamma/gamma-prime phase equilibrium in the nickel-aluminum system

A theoretical model is proposed for the determination of phase equilibrium in alloys, taking into consideration dissimilar lattice parameters. Volume-dependent pair interactions are introduced by means of phenomenological Lennard-Jones potentials and the configurational entropy of the system is treated in the tetrahedron approximation of the cluster variation method. The model is applied to the superalloy-relevant, nickel-rich, gamma/gamma-prime phase region of the Ni-Al phase diagram. The model predicts reasonable values for the lattice parameters and the enthalpy of formation as a function of composition, and the calculated phase diagram closely approximates the experimental diagram.

Sanchez, J. M.↗

A model of the photosynthetically available and usable irradiance in the sea

A theoretical model describing the depth dependence of the solar irradiance available to phytoplankton for photosynthesis is developed for waters classified as Case I by Jerlov (1976). The techniques used to account for the effects of incident solar irradiance, pigment concentration, and the spectral diffuse attentuation coefficient are described; an expression for the photosynthetically usable irradiance is derived; and particular attention is given to the specific diffuse absorption coefficient for chlorophyll (Morel, 1978). The relationships among the primary model parameters are shown in graphs.

Collins, Donald J.↗

Modeling of Radiative Heating in Base Region of Jovian Entry Probe

A theoretical model is derived to determine the average thermodynamic properties in the expanding region, recirculating region, recompression region, and neck region through application of one-dimensional conservation equations. Radiative transfer is calculated using spectrally detailed computer codes accounting for nonequilibrium. The results show that the most severe heating occurs immediately behind the frustum, and that the recompression and neck regions are the major sources of radiation that heats the base stagnation point, The radiation flux to the base point is slightly stronger with ablation than without. Its value is 0.11(43 P(sub b)/P(sub s))(sup 2) times that to the front stagnation point where the base pressure P(sub b) is defined as the average pressure in the recirculating region and P(sub s) is the front stagnation-point pressure. The time-integrated heat load to the base point is 18(43 P(sub b)/P(sub s))(sup 2) kJ/sq cm.

Park, Chul↗

Fifteen Years of Laboratory Astrophysics at Ames

Tremendous strides have been made in our understanding of interstellar material over the past fifteen years thanks to significant, parallel developments in two closely related areas: observational astronomy and laboratory astrophysics. Fifteen years ago the composition of interstellar dust was largely guessed at, the concept of ices in dense molecular clouds ignored, and the notion of large, abundant, gas phase, carbon-rich molecules widespread throughout the interstellar medium (ISM) considered impossible. Today the composition of dust in the diffuse ISM is reasonably well constrained to cold refractory materials comprised of amorphous and crystalline silicates mixed with an amorphous carbonaceous material containing aromatic structural units and short, branched aliphatic chains. In the dense ISM, these cold dust particles are coated with mixed-molecular ices whose compositions are very well known. Lastly, the signature of carbon-rich polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by early interstellar chemistry standards, is widespread throughout the ISM. This great progress has only been made possible by the close collaboration of laboratory experimentalists with observers and theoreticians, all with the goal of applying their skills to astrophysical problems of direct interest to NASA programs. Such highly interdisciplinary collaborations ensure fundamental, in depth coverage of the wide-ranging challenges posed by astrophysics. These challenges include designing astrophysically focused experiments and data analysis, tightly coupled with astrophysical searches spanning 2 orders of magnitude in wavelength, and detailed theoretical modeling. The impact of our laboratory has been particularly effective as there is constant cross-talk and feedback between quantum theorists; theoretical astrophysicists and chemists; experimental physicists; organic, physical and petroleum chemists; and infrared and UV/Vis astronomers. In this paper, two examples of the Ames Program will be given. We have been involved in identifying 9 out of the 14 interstellar pre-cometary ice species known, determined their abundances and the physical nature of the ice structure. Details on our ice work are given in the paper by Sandford et al. Our group is among the pioneers of the PAH model. We built the theoretical framework, participated in the observations and developed the experimental techniques needed to test the model. We demonstrated that the ubiquitous infrared emission spectrum associated with many interstellar objects can be matched by laboratory spectra of neutral and positively charged PAHs and that PAHs were excellent candidates for the diffuse interstellar band (DIB) carriers. See Salama et al. and Hudgins et al.

Allamandola, L. J.↗

Ion dynamics in the Venus ionosphere

Measurement data on the ion velocity in the Venus ionosphere (mainly from the Pioneer Venus Orbiter Retarding Potential Analyzer) are summarized, and theoretical models developed to explain them are reviewed. Data and theoretical predictions are compared in extensive graphs and diagrams and discussed in detail. It is shown that the predominant flow is away from the subsolar point, at up to 3 km/sec in the terminator region. A model of axisymmetric flow based on momentum, energy, and mass conservation laws is found to reproduce the observed ion velocities at solar zenith angles less than about 140 deg, but not the high velocities and chaotic behavior seen near the antisolar point. Also discussed are significant differences between the flow above and below about 400 km and the effects of changes in the dynamic pressure of the solar wind.

Miller, K. L.↗

Evaluation of a composite mobile holographic nondestructive test system

A simplified theoretical model for the interpretation of the double-exposure holographic interference fringe loci due to the general three-dimensional displacements was derived for the specific composite mobile holographic nondestructive test system. The model, representing a good approximation to a more tedious theoretical result, predicts that a combination of in-plane and out-of-plane displacements of the surface will produce concentric circular-shaped fringe patterns with locations of their center affected by the displacements. Appropriate experiments were designed and carried out for the test of the validity of the theory. These experiments include the taking of double-exposure holograms of in-plane translations and combined in-plane and out-of-plane translations. The simplified model agreed quite well with the experimental results. Experimentally observed effects due to the curvature of the test plate and the variations of the angles of incidence of the laser light suggest that in order for the simplified model to be able to predict the test results more accurately, incidence and reflection of the laser light should be chosen as nearly perpendicular to the surface of the tested object as possible.

Liu, H. K.↗

Hydrodechlorination of 1,2-Dichloroethane on Platinum Catalysts: Insights from Reaction Kinetics Experiments, Density Functional Theory, and Microkinetic Modeling

Catalytic hydrodechlorination is a promising strategy for treating industrial 1,2-dichloroethane wastes, for which Pt and Pt-based alloy catalysts are widely used. Here, we performed a detailed mechanistic study for 1,2-dichloroethane hydrodechlorination on Pt using a synergistic approach combining density functional theory (DFT) calculations, reaction kinetics experiments, and microkinetic modeling. Using planewave DFT calculations, we evaluated the reaction energy and activation energy barrier of each elementary step involved in the reaction network on Pt(111). The calculated energetics were then incorporated into a comprehensive mean-field microkinetic model accounting for a total of 65 elementary steps. The model-predicted reaction rates were compared with the results from our reaction kinetics experiments on SiO2-supported Pt catalysts. Our results indicated that the hydrodechlorination of 1,2-dichloroethane on Pt(111) starts with a H-removal step; then, it proceeds through a sequence of alternating dechlorination and dehydrogenation steps until vinylidene (CH 2 C*) is formed; finally, CH 2 C* is hydrogenated to the final product, ethane, sequentially via vinyl (CH 2 CH*), ethylene, and ethyl (CH 3 CH 2 *) intermediates. After model parameter adjustments, we achieved good agreement between our theoretical model and experimental results; the adjustments to the calculated parameters are consistent with the typically anticipated coverage effects. Furthermore, our study offers valuable mechanistic insights, which are useful for improving catalysts for this chemistry.

1,2-dichloroethane↗