Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Chemical reaction dynamics”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 469 records · Page 26

Ultrafast studies of elusive chemical reactions in the gas phase

The chemical composition of the interstellar medium and planetary atmospheres is constantly in flux as atoms and molecules collide and interact with high-energy particles such as electrons, protons, and photons. These transformative processes ultimately lead to the coalescence of molecules and eventually the birth of stars. Our understanding of these chemical ecosystems relies on models that synthesize data from gas-phase experiments, providing insights into reaction cross sections. This Review examines efforts to delve into the fundamental bond-forming and bond-breaking dynamics that occur during bimolecular and electron-initiated reactions. Furthermore, these experiments involve clever approaches to establish a time reference and the collision geometry necessary for tracking atomic motion with femtosecond time resolution. Findings from these efforts enhance present models and improve predictions for molecule-molecule and electron-molecule collisions.

74 ATOMIC AND MOLECULAR PHYSICS↗

Aging phenomena in the two-dimensional complex Ginzburg-Landau equation

The complex Ginzburg-Landau equation with additive noise is a stochastic partial differential equation that describes a remarkably wide range of physical systems which include coupled non-linear oscillators subject to external noise near a Hopf bifurcation instability and spontaneous structure formation in non-equilibrium systems, e.g., in cyclically competing populations or oscillatory chemical reactions. Here, we employ a finite-difference method to numerically solve the noisy complex Ginzburg-Landau equation on a two-dimensional domain with the goal to investigate its non-equilibrium dynamics when the system is quenched into the “defocusing spiral quadrant”. We observe slow coarsening dynamics as oppositely charged topological defects annihilate each other, and characterize the ensuing aging scaling behavior. We conclude that the physical aging features in this system are governed by non-universal aging scaling exponents. We also investigate systems with control parameters residing in the “focusing quadrant”, and identify slow aging kinetics in that regime as well. Finally, we provide heuristic criteria for the existence of slow coarsening dynamics and physical aging behavior in the complex Ginzburg-Landau equation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Three-dimensional modelling of trace species in the Arctic lower stratosphere

A three-dimensional radiative-dynamical-chemical model has been developed and used to study some aspects of modeling the polar lower stratosphere. The model includes a comprehensive gas-phase chemistry scheme as well as a treatment of heterogeneous reactions occurring on the surface of polar stratospheric clouds. Tracer transport is treated by an accurate, nondispersive scheme with little diffusion suited to the representation of strong gradients. Results from a model simulation of early February 1990 are presented and used to illustrate the importance of the model transport scheme. The model simulation is also used to examine the potential for Arctic ozone destruction and the relative contributions of the chemical cycles responsible.

Chipperfield, Martyn↗

Field-aligned dynamics of chemically induced perturbations to the ionosphere

Ionospheric modification using photochemically reactive vapors is studied with a one-dimensional, multiion, fluid model of plasma flow along magnetic field lines. The magnitudes of ion and electron density changes are determined by considering both chemical processes (i.e., photoionization, ion-molecule reactions, dissociative recombination, electron attachment) and transport processes (i.e., multispecies diffusion, electric currents, ambipolar electric fields). The numerical treatment in the model is not specific to any type of release or any interaction chemistry. It has been used to simulate releases of Ba, CO2, and CF3Br in the ionosphere, but generalization to other species may be easily accomplished. The results of the calculations are found to be in good agreement with experimental observations. The feasibility of modifying the parallel current paths in the auroral F region is examined.

Bernhardt, P. A.↗

Sensitivity study of coupled chemical-CFD simulations for analyzing aluminum-clad spent nuclear fuel storage in sealed canisters

We report the United States Department of Energy (DOE) manages over 50 Metric Tons Heavy Metal (MTHM) of aluminum-clad spent nuclear fuel. One main source for DOE’s Aluminum-clad spent nuclear fuel (ASNF) inventory is the advanced test reactor (ATR) at the INL site, which makes this fuel of particular interest for storage scenarios. Road-ready and final disposition packaging configurations for the ATR fuel dictates storage within helium-backfilled, sealed DOE standard canisters. The conditions within these sealed canisters for extended (greater than50 year dry) storage is of interest. To further this goal, a three-dimensional (3D) multi-physics computational fluid dynamics (CFD) model is developed of the sealed DOE standard canisters. This 3D CFD model is one-way coupled with bulk gas radiolysis reactions considering sealed canisters with inert gas and possible trace amounts of air and water vapor. This study looks at the evolution of the thermal history of the canisters over a 50 year time period with a coupling to the chemical reactions occurring from radiolytic breakdown of residual water. A sensitivity study is then carried out over the parameters of the model including the fuel decay heat, residual water content, sealed pressure, canister external temperature, and canister emissivity. In pure helium, hydrogen generation rates are low, under 10 ppm, but hydrogen generation rates are affected greatly by the presence of even 1% residual air, increasing by 50-plus-fold, and nitric acid generation with residual air also occurs ranging from 500 to 4000 ppm after 50 years. The fuel decay heat and the residual water content show the most importance in the generation of hydrogen gas in pure air, and for nitric acid with a residual air condition. External temperature, canister emissivity and sealed pressure all show minor sensitivity effects to the generation of potentially harmful species.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

MISPR : an open-source package for high-throughput multiscale molecular simulations

Computational tools provide a unique opportunity to study and design optimal materials by enhancing our ability to comprehend the connections between their atomistic structure and functional properties. However, designing materials with tailored functionalities is complicated due to the necessity to integrate various computational-chemistry software (not necessarily compatible with one another), the heterogeneous nature of the generated data, and the need to explore vast chemical and parameter spaces. The latter is especially important to avoid bias in scattered data points-based models and derive statistical trends only accessible by systematic datasets. Here, we introduce a robust high-throughput multi-scale computational infrastructure coined MISPR (Materials Informatics for Structure–Property Relationships) that seamlessly integrates classical molecular dynamics (MD) simulations with density functional theory (DFT). By enabling high-performance data analytics and coupling between different methods and scales, MISPR addresses critical challenges arising from the needs of automated workflow management and data provenance recording. The major features of MISPR include automated DFT and MD simulations, error handling, derivation of molecular and ensemble properties, and creation of output databases that organize results from individual calculations to enable reproducibility and transparency. In this work, we describe fully automated DFT workflows implemented in MISPR to compute various properties such as nuclear magnetic resonance chemical shift, binding energy, bond dissociation energy, and redox potential with support for multiple methods such as electron transfer and proton-coupled electron transfer reactions. The infrastructure also enables the characterization of large-scale ensemble properties by providing MD workflows that calculate a wide range of structural and dynamical properties in liquid solutions. MISPR employs the methodologies of materials informatics to facilitate understanding and prediction of phenomenological structure–property relationships, which are crucial to designing novel optimal materials for numerous scientific applications and engineering technologies.

36 MATERIALS SCIENCE↗

Prediction of local concentration fields in porous media with chemical reaction using a multi scale convolutional neural network

The study of solute transport in porous media is of interest in many chemical engineering systems. Some example applications include packed bed catalytic reactors, filtration devices, and batteries. The pore scale modeling of these systems is time consuming and may require large computing resources, for this reason computational fluid dynamics (CFD) simulations are not practical if a large number of simulations is required, like in multiscale modeling, where a model at a large scale calls for pore scale simulations. It has been shown that neural networks can be trained with a dataset of flow simulations and then predict fields orders of magnitude faster, and with less computational resources, in new domains. However, it is crucial to provide the neural network with an effective description of the domain and the undergoing operating conditions to be able to train models that generalize accurately in unseen samples. Therefore, research is needed to employ neural networks in new complex systems. The appropriate training of a network for predicting coupled flow and solute transport processes is an outstanding problem due to the complex interplay between geometry and operating conditions. In this work, we train a multi scale convolutional neural network (MSNet) with a diverse dataset of simulations of transport and chemical reaction in porous media to predict the local concentration fields in images of porous media. Our dataset contains a wide diversity of sphere pack arrangements under different operating conditions (Péclet and Reynolds numbers). Further, we train a robust model by employing different input descriptors that represent the medium and the different operating conditions of each system. Our trained model is able to provide nearly instantaneous predictions, compared to around twenty hours of the CFD workflow, with less than 3.5% error on new geometries and transport conditions. Thus the model could be easily integrated in a multiscale workflow where fast response is needed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Off-Stoichiometric Restructuring and Sliding Dynamics of Hexagonal Boron Nitride Edges in Conditions of Oxidative Dehydrogenation of Propane

Boron-containing materials, such as hexagonal boron nitride (h-BN), recently shown to be active and selective catalysts for the oxidative dehydrogenation of propane (ODHP), have been shown to undergo significant surface oxyfunctionalization and restructuring. Although experimental ex situ studies have probed the change in chemical environment on the surface, the structural evolution of it under varying reaction conditions has not been established. Herein, we perform global optimization structure search with a grand canonical genetic algorithm to explore the chemical space of off-stoichiometric restructuring of the h-BN surface under ambient as well as ODHP-relevant conditions. A grand canonical ensemble representation of the surface is established, and the predicted 11B solid-state NMR spectra are consistent with previous experimental reports. In addition, we investigated the relative sliding of h-BN sheets and how it influences the surface chemistry with ab initio molecular dynamics simulations. Furthermore, the B–O linkages on the edges are found to be significantly strained during the sliding, causing the metastable sliding configurations to have higher reactivity toward the activation of propane and water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Project ERIC - The search for environmental reactions induced by comets

A sounding rocket experiment was conducted to release molecules of H2O and CO2 into the daytime ionosphere within the simultaneous fields of view of the Millstone Hill radar and the Dynamics Explorer UV imager. Preliminary results confirm the creation of chemically-induced F-region plasma depletions and reduced UV intensities from the modified region.

Mendillo, Michael↗

The possible role of soluble salts in chemical evolution

A model for a prebiotic environment in which concentration, condensation, and chemical evolution of biomolecules could have occurred is proposed. The principal reactions expected of proteins, nucleic acids, lipids, and some of their precursors in this environment are discussed. The model is based on the concept of a fluctuating system in which hydration and dehydration processes occur in a cyclic manner, with allowance for high concentrations of soluble salts, such as chlorides and sulfates. It is concluded that the proposed prebiotic environment with its dynamical characteristics is a plausible model for the chemical evolution from biomonomers through random oligomers toward self-replicating chemical systems.

Lahav, N.↗

Mechanisms of Alkali Ionic Transport in Amorphous Oxyhalides Solid State Conductors

Amorphous oxyhalides have attracted significant attention due to their relatively high ionic conductivity (1 mS cm –1 ), excellent chemical stability, mechanical softness, and facile synthesis routes via standard solid‐state reactions. These materials exhibit an ionic conductivity that is almost independent of the underlying chemistry, in stark contrast to what occurs in crystalline conductors. In this work, we employ machine learning interatomic potentials to construct large‐scale molecular dynamics trajectories encompassing hundreds of nanoseconds to obtain statistically converged transport properties. We find that the amorphous state consists of chain fragments of metal‐anion tetrahedra of various lengths. By analyzing the residence time of alkali cations migrating around tetrahedrally‐coordinated metals, we find that oxygen anions limit alkali diffusion. By computing the full Einstein expression of the ionic conductivity, we demonstrate that the alkali transference number of these materials is strongly influenced by distinct‐particles correlations, while alkali transport is dictated by uncorrelated self‐diffusion. By extending this analysis to chemical compositions AMX 2.5 O 0.75 , spanning different alkaline (A = Li, Na, K), metallic (M = Al, Ga, In), and halogen (X = Cl, Br, I) species, we clarify why the diffusion properties of these materials remain largely insensitive to variations in atomic isovalent chemistry.

amorphous materials↗

Tracing the transient reaction kinetics of adsorbed species by in situ/operando infrared spectroscopy

The dynamic reaction behavior (i.e., transient responses) of IR-observable adsorbed species and gaseous products obtained from transient kinetic studies provide valuable kinetic and mechanistic information, namely: the abundance of active intermediates and their reactivity distribution, the chemical structure of IR-observable active and spectator species, the sequence of their formation, and the kinetically significant and rate-determining step under reaction conditions of practical catalysis. We discuss the use of transient response data to elucidate the reaction mechanisms of several gas-solid reactions: CO/H 2 , CO/H 2 /C 2 H 4 , photocatalytic oxidation of ethanol, and the CO 2 -amine reaction. The IR coupled with transient kinetic techniques is especially useful for investigating the mechanisms of photocatalytic reactions because both photogenerated electrons and many adsorbed species are IR-active (exhibiting measurable IR bands), and their evolution occurs on a time scale of seconds at ambient temperature. We highlight the key features and limitations of in situ IR with transient kinetics, as well as their significance in catalyst design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hidden features in the OH-stretching spectra of amino acid decorated air–water interfaces

Chemical reactivity at the air–water interface is governed by the interfacial solvation of reactive species. For instance, during aqueous amino acid-based CO 2 absorption, water reorganizes around the reactive sites and couples dynamically with reaction pathways, facilitating the reaction. In this context, surface-sensitive vibrational sum-frequency generation (vSFG) spectroscopy can probe the OH stretch vibrations of interfacial water and determine the solvation structures around reactants and products, thereby furthering our understanding of the role of interfacial solvation. However, vSFG spectra of the air–water interface in the presence of charged species can be remarkably complex; key species-bound local water structures with distinct orientations may be hidden beneath prominent vSFG peaks arising from water–water hydrogen bonds and remain difficult to resolve. Here, we measure and compute vSFG spectra of the water OH stretch at air–water interfaces decorated with amino acids in their zwitterionic and anionic forms, as well as equimolar mixtures of these forms with bicarbonate. The latter represents post-CO 2 -absorption conditions. We find that computing depth- and frequency-dependent spectral densities—decomposed into contributions from water molecules hydrogen-bonded exclusively to other water molecules, exclusively to amines, exclusively to carboxylates, or shared between these polar/charged groups—is indispensable for accurate interpretation of the vSFG spectra. Key findings include orientational flip-flop in water sub-layers, strong carboxylate-water H-bonding, and water orientational ordering extending into the bulk aqueous phase induced by anionic amino acids. Here, this study provides a computational spectroscopic platform for improved understanding of interfacial solvation relevant to interfacial reactivity.

Air-water interface↗

Diffusion power spectra as a window into dynamic materials architecture

Chemical recycling of commodity and specialty polymers presents a multifaceted challenge for industrial societies. On one hand, macromolecular architectures must be engineered to yield durable products that, on the other hand, rapidly deconstruct to recyclable monomers under pre-determined conditions. Polymer deconstruction is a chemical process that requires deep understanding of molecular reactivity in heterogeneous media, where porous material architectures evolve in both space and time. To build this understanding, we develop herein experimental and analytical methods describing sets of diffusive eigenmodes that exist within time-varying, non-Euclidean boundary conditions, a situation commonly encountered in the reactive deconstruction of polymers where chain fragments splay, alter their local dynamics, and evolve in their confinement of reacting media. Diffusion power spectra, discerned experimentally by NMR, yield polymer and solvent frequency-domain velocity autocorrelation functions that are analyzed in the context of physical models for chemical reactions parameterized with fractal mathematics. The results connect local motion in polymers to chemical reactivity during acidolysis of circular elastomers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Trends from the Long-term Data Record and Models: What Do They Tell Us About our Ability to Predict Ozone Recovery?

Our industrial society has performed an experiment on the stratospheric ozone layer over the last several decades. The initial part of this experiment was the rapidly increasing release of halogen-containing compounds that carry chlorine and bromine to the stratosphere where they can cause a loss of ozone. The present part of this experiment is the implementation of the Montreal Protocol, which has led to a leveling off of these halogen compounds and the beginning of their slow removal from the atmosphere. The observation and attribution of ozone response to the halogens has been a particularly important and difficult task because of the impact of solar cycle uv variation, two major volcanic eruptions (El Chichon and Pinatubo), and interannual dynamic variability of the stratosphere. We have run 3 different simulations of the chemistry and transport of ozone and the minor constituents that affect ozone to help evaluate our understanding of the causes of ozone change and to assess our ability to predict ozone recovery with the removal of halogens from the stratosphere. One simulation, using the Goddard chemical transport model (CTM), had interannual variability in the dynamics for the entire 50 years of simulation, which included the past 3 decades (1974-2004) and the next 2 decades to 2022. The other two simulations used the Global Modeling Initiative (GMI) CTM with no dynamical variability: one used a the winds and temperatures from a repeating warm Arctic winter and the other used a repeating cold Arctic winter. All simulations included the effects of aerosol surfaces from volcanic eruptions on chemical reactions as well as the variation in UV over the 11-year solar cycle.

Strahan, Susan↗

On the influence of over-parameterization in manifold based surrogates and deep neural operators

Constructing accurate and generalizable approximators (surrogate models) for complex physico-chemical processes exhibiting highly non-smooth dynamics is challenging. The main question is what type of surrogate models we should construct and should these models be under-parameterized or over-parameterized. In this work, we propose new developments and perform comparisons for two promising approaches: manifold-based polynomial chaos expansion (m-PCE) and the deep neural operator (DeepONet), and we examine the effect of over-parameterization on generalization. While m-PCE enables the construction of a mapping by first identifying low-dimensional embeddings of the input functions, parameters, and quantities of interest (QoIs), a neural operator learns the nonlinear mapping via the use of deep neural networks. Here, we demonstrate the performance of these methods in terms of generalization accuracy by solving the 2D time-dependent Brusselator reaction-diffusion system with uncertainty sources, modeling an autocatalytic chemical reaction between two species. We first propose an extension of the m-PCE by constructing a mapping between latent spaces formed by two separate embeddings of the input functions and the output QoIs. To further enhance the accuracy of the DeepONet, we introduce weight self-adaptivity in the loss function. We demonstrate that the performance of m-PCE and DeepONet is comparable for cases of relatively smooth input-output mappings. However, when highly non-smooth dynamics is considered, DeepONet shows higher approximation accuracy. We also find that for m-PCE, modest over-parameterization leads to better generalization, both within and outside of distribution, whereas aggressive over-parameterization leads to over-fitting. In contrast, an even highly over-parameterized DeepONet leads to better generalization for both smooth and non-smooth dynamics. Furthermore, we compare the performance of the above models with another recently proposed operator learning model, the Fourier Neural Operator, and show that its over-parameterization also leads to better generalization. Taken together, our studies show that m-PCE can provide very good accuracy at very low training cost, whereas a highly over-parameterized DeepONet can provide better accuracy and robustness to noise but at higher training cost. In both methods, the inference cost is negligible.

97 MATHEMATICS AND COMPUTING↗

A scalable solid-state nanoporous network with atomic-level interaction design for carbon dioxide capture

Carbon capture and sequestration reduces carbon dioxide emissions and is critical in accomplishing carbon neutrality targets. Here, we demonstrate new sustainable, solid-state, polyamine-appended, cyanuric acid–stabilized melamine nanoporous networks (MNNs) via dynamic combinatorial chemistry (DCC) at the kilogram scale toward effective and high-capacity carbon dioxide capture. Polyamine-appended MNNs reaction mechanisms with carbon dioxide were elucidated with double-level DCC where two-dimensional heteronuclear chemical shift correlation nuclear magnetic resonance spectroscopy was performed to demonstrate the interatomic interactions. We distinguished ammonium carbamate pairs and a mix of ammonium carbamate and carbamic acid during carbon dioxide chemisorption. The coordination of polyamine and cyanuric acid modification endows MNNs with high adsorption capacity (1.82 millimoles per gram at 1 bar), fast adsorption time (less than 1 minute), low price, and extraordinary stability to cycling by flue gas. This work creates a general industrialization method toward carbon dioxide capture via DCC atomic-level design strategies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗