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Predicting CaO-(MgO)-Al2O3-SiO2 glass reactivity in alkaline environments from force field molecular dynamics simulations
In this investigation, force field-based molecular dynamics (MD) simulations have been employed to generate detailed structural representations for a range of amorphous quaternary CaO-MgO-Al{sub 2}O{sub 3}-SiO{sub 2} (CMAS) and ternary CaO-Al{sub 2}O{sub 3}-SiO{sub 2} (CAS) glasses. Comparison of the simulation results with select experimental X-ray and neutron total scattering and literature data reveals that the MD-generated structures have captured the key structural features of these CMAS and CAS glasses. Based on the MD-generated structural representations, we have developed two structural descriptors, specifically (i) average metal oxide dissociation energy (AMODE) and (ii) average self-diffusion coefficient (ASDC) of all the atoms at melting. Both structural descriptors are seen to more accurately predict the relative glass reactivity than the commonly used degree of depolymerization parameter, especially for the eight synthetic CAS glasses that span a wide compositional range. Hence these descriptors hold great promise for predicting CMAS and CAS glass reactivity in alkaline environments from compositional information.
Molecular Simulation of Lithium Carbonate Reactive Vapor–Liquid Equilibria Using a Deep Potential Model
We developed a first-principles machine learning model for the reactive vapor–liquid phase behavior of molten Li 2 CO 3 . The model was trained on ab initio electronic density functional theory data using the Deep Potential (DP) methodology, and its accuracy was evaluated by comparing model predictions of density and viscosity to experimental measurements. Direct coexistence simulations with the DP model over time scales of tens of nanoseconds were used to observe equilibrium dissociation of Li 2 CO 3 into CO 2 residing primarily in the vapor phase and Li 2 O which remains dissolved in the liquid. The simulations covered a range of temperatures, overall system sizes, and vapor-to-liquid volume ratios. Results were analyzed in terms of the observed chemical composition of the liquid and vapor phases, product structure, and CO 2 partial pressures. In addition, we calculated equilibrium constants for the dissociation reaction by assuming ideal-solution behavior for the liquid. As expected on the basis of thermodynamic arguments and prior experiments for this system, the observed partial pressure of CO 2 in the gas phase depends on both the temperature and the ratio of vapor to liquid volumes, while the calculated equilibrium constants only depend on temperature. DP model predictions for the equilibrium constant of the reaction are generally consistent with the available experimental measurements. Furthermore, the present study establishes the validity of the DP methodology for the description of reactive, multiphase equilibria from first principles, with possible applications to many other systems of scientific and technological interest even in the absence of relevant experimental measurements.
Enabling Efficient and Accurate Computational Studies of MOF Reactivity via QM/MM and QM/QM Methods
Electronic structure calculations can provide unique insight into metal–organic framework (MOF) reactivity and defect formation. Such calculations can be broadly categorized as utilizing either periodic or cluster models, each with their respective advantages and disadvantages. In the present study, we demonstrate how multiscale methods can leverage the advantages of both approaches to enable high levels of accuracy and computational efficiency in studies of MOF reactivity. Using defect formation in a zeolitic imidazolate framework (ZIF) as a prototypical example, we benchmark a quantum mechanics/molecular mechanics (QM/MM) scheme that enables highly efficient cluster-based calculations on MOFs. We demonstrate the importance of correctly accounting for the influence of both dative bond cleavage in the QM cluster and long-range mechanical coupling to the bulk to achieving accurate QM/MM studies of MOFs. We subsequently leverage these cluster models in a QM/QM scheme that goes beyond standard DFT to yield “gold-standard” correlated wave function results on MOFs at modest computational cost. Crucially, we find several cases in which the incorporation of these correlated corrections yields qualitatively important corrections over conventional DFT values.
Multiscale Reactive Model for 1,3,5-Triamino-2,4,6-trinitrobenzene Inferred by Reactive MD Simulations and Unsupervised Learning
When high-energy-density materials are subjected to thermal or mechanical insults at extreme conditions (shock loading), a coupled response between the thermo-mechanical and chemical behaviors is systematically induced. Herein we develop a reaction model for the fast chemistry of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) at the mesoscopic scale, where the chemical behavior is determined by underlying microscopic reactive simulations. The slow carbon cluster formation is not discussed in the present work. All-atom reactive molecular dynamics (MD) simulations are performed with the ReaxFF potential, and a reduced-order chemical kinetics model for TATB is fitted to isothermal and adiabatic simulations of single crystal chemical decomposition. Unsupervised machine learning techniques based on non-negative matrix factorization are applied to MD trajectories to model the decomposition kinetics of TATB in terms of a four-component model. The associated heats of reaction are fit to the temperature evolution from adiabatic decomposition trajectories. Using a chemical species analysis, we show that non-negative matrix factorization captures the main chemical decomposition steps of TATB and provides an accurate estimation of their evolution with temperature. The final analytical formulation, coupled to a diffusion term, is incorporated into a continuum formalism, and simulation results are compared one-to-one against MD simulations of 1D reaction propagation along different crystallographic directions and with different initial temperatures. A good agreement is found for both the temporal and spatial evolution of the temperature field.
Nanoscale control over water-film thickness using temperature modulation: tuning mineral carbonation reactivity
Temperature modulation was demonstrated as a novel way to control water partitioning during the reaction of silicate minerals with water-saturated supercritical carbon dioxide.
The photoionization of methoxymethanol: Fingerprinting a reactive C 2 oxygenate in a complex reactive mixture
Methoxymethanol (CH 3 OCH 2 OH) is a reactive C 2 ether-alcohol that is formed by coupling events in both heterogeneous and homogeneous systems. It is found in complex reactive environments—for example those associated with catalytic reactors, combustion systems, and liquid-phase mixtures of oxygenates. Using tunable synchrotron-generated vacuum-ultraviolet photons between 10.0 and 11.5 eV, we report on the photoionization spectroscopy of methoxymethanol. We determine that the lowest-energy photoionization process is the dissociative ionization of methoxymethanol via H-atom loss to produce [C 2 H 5 O 2 ] + , a fragment cation with a mass-to-charge ratio (m/z) = 61.029. Here, we measure the appearance energy of this fragment ion to be 10.24 ± 0.05 eV. The parent cation is not detected in the energy range examined. To elucidate the origin of the m/z = 61.029 (C 2 H 5 O 2 ) fragment, we used automated electronic structure calculations to identify key stationary points on the cation potential energy surface and compute conformer-specific microcanonical rate coefficients for the important unimolecular processes. The calculated H-atom dissociation pathway results in a [C 2 H 5 O 2 ] + fragment appearance at 10.21 eV, in excellent agreement with experimental results.
Non-partial wave treatment of reactive and non-reactive scattering Coupled integral equation formalism.
Coupled integral equations are derived for the full scattering amplitudes for both reactive and nonreactive channels. The equations do not involve any partial wave expansion and are obtained using channel operators for reactive and nonreactive collisions. These coupled integral equations are similar in nature to equations derived for purely nonreactive collisions of structureless particles. Using numerical quadrature techniques, these equations may be reduced to simultaneous algebraic equations which may then be solved.
On the modelling of non-reactive and reactive turbulent combustor flows
A study of non-reactive and reactive axisymmetric combustor flows with and without swirl is presented. Closure of the Reynolds equations is achieved by three models: kappa-epsilon, algebraic stress and Reynolds stress closure. Performance of two locally nonequilibrium and one equilibrium algebraic stress models is analyzed assuming four pressure strain models. A comparison is also made of the performance of a high and a low Reynolds number model for combustor flow calculations using Reynolds stress closures. Effects of diffusion and pressure-strain models on these closures are also investigated. Two models for the scalar transport are presented. One employs the second-moment closure which solves the transport equations for the scalar fluxes, while the other solves the algebraic equations for the scalar fluxes. In addition, two cases of non-premixed and one case of premixed combustion are considered. Fast- and finite-rate chemistry models are applied to non-premixed combustion. Both show promise for application in gas turbine combustors. However, finite rate chemistry models need to be examined to establish a suitable coupling of the heat release effects on turbulence field and rate constants.
Conceptual Design of Passive Neutron Albedo Reactivity and Active Neutron Albedo Reactivity Instruments for Various Arrangements of Pebble Bed Reactor Pebbles
MCNP6 simulations were performed to assess the anticipated capability of the Passive Neutron Albedo Reactivity technique for nuclear safeguards measurements of irradiated pebble/pebbles. Two physical setups were examined. One with a single pebble of three different burnups and one with 27 pebbles in a cube. For all cases the sensitivity to removing all the fissile material was examined. For both of the physical setups, 4 assay cases were examined: (a) singles count rates for which the only source neutrons were the inherent neutrons in the fuel, (b) singles count rates again except this time two relatively weak AmLi sources were placed above and below the top central pebble and the combined effect of both neutron source terms were examined, (c) doubles count rates for which the only source neutrons were the inherent neutrons in the fuel, and (d) doubles count rates again except this time two relatively weak AmLi sources were placed above and below the top central pebble and the combined effect of both neutron source terms were examined. Finally, a few parameters such as Cd near the 3 He tubes were perturbed to see if the results could be improved.
Reactivity with Water and Bulk Ruthenium Redox of Lithium Ruthenate in Basic Solutions
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Explaining persistent incomplete mixing in multicomponent reactive transport with Eulerian stochastic model
We present an Eulerian stochastic advection–diffusion–reaction (SADR) model and use it to explain incomplete mixing typically observed in transport experiments with bimolecular reactions. Unlike traditional advection– dispersion–reaction (ADR) models, the SADR model describes mechanical and diffusive mixing as two separate processes. In the SADR model, mechanical mixing is driven by random advective velocity whose variance is given by the coefficient of mechanical dispersion. The diffusive mixing is modeled as a Fickian diffusion process with the effective diffusion coefficient. We demonstrate that the sum of the two coefficients is equal to the dispersion coefficient, but only the effective diffusion coefficient contributes to the mixing-controlled reactions. We use experimental results of Gramling et al. * * to show that for transport and bimolecular reactions in porous media, the SADR model is significantly more accurate than the ADR model, which overestimates the concentration of the reaction product by as much as 60%. We also show that the SADR model predicts an experimentally observed bell- shaped spatial distribution of the reactive product concentration, while the ADR model results in a concentration distribution with an unphysical kink.
Reactive oxygen species alter chemical composition and adsorptive fractionation of soil organic matter
Reactive oxygen species (ROS), formed during redox fluctuations in iron-rich soils, have been known to stimulate lignin degradation, although not much is known about how they alter soil organic matter (SOM) composition and interaction with mineral surfaces. We conducted a laboratory experiment to see how ROS altered SOM composition and adsorptive fractionation onto Fe-mineral surfaces. We reacted water extracts of SOM with ·OH, produced by the Fenton reaction, and then conducted a sorption experiment of the extracts with goethite to analyze the amount and quality of SOM adsorbed. The Fenton reaction preferentially consumed low-O, mostly aromatic molecules, and new high-O molecules were detected post-Fenton, nearly half of which were carbohydrate-like. Although the amount of C adsorbed did not change after oxidation, the post-Fenton adsorbed molecules were more oxidized. Pre-Fenton adsorption was dominated by aromatic molecules (90%), but post-Fenton, the adsorbed molecules were 75% aromatic and 25% carbohydrate-like. We show that the ·OH radical oxidized SOM and shifted patterns of adsorption to a more oxidized pool. Because adsorption to minerals is thought to stabilize SOM, our results suggest that ROS may alter the availability and stabilization patterns of SOM.
Structure and reactivity of sodium aluminate complexes in alkaline solutions
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Synthesis of [60]- and [70]Fullerene-Fused Tetrahydroquinoxaline Derivatives by Oxidative [4 + 2] Cycloaddition with Unusual Reactivity and Regioselectivity
The oxidative [4 + 2] reaction of o-phenylenediamine-derived disulfonamides with fullerene C 60 and C 70 is reported, in which electron-deficient reactants showed high reactivity. The reaction of C 70 exhibited unusual regioselectivity, yielding a [5,6]-adduct as the major product, which was characterized by 1 H, 13 C NMR and single-crystal X-ray diffraction. Here, DFT calculations revealed the reaction is an inverse-electron-demand Diels–Alder (IEDDA) reaction, and the [5,6]-adduct of C 70 is a kinetic product.
Plasma-Catalyst Reactivity Control of Surface Nitrogen Species through Plasma-Temperature-Programmed Hydrogenation to Ammonia
Nonthermal plasma activation of N 2 can facilitate nitrogen adsorption on metal catalysts at low bulk temperatures and atmospheric pressure. Here, we apply a plasma-assisted temperature-programmed reaction (plasma-TPRxn) for ammonia (NH 3 ) synthesis using sequential exposure of a silica-supported metal catalyst to N 2 plasma followed by thermal hydrogen treatment while ramping the temperature to decouple the plasma activation of N 2 from surface catalyzed hydrogenation steps. This approach eliminates the effects from bulk plasma phase reactions, thereby allowing for direct interrogation of plasma activated nitrogen on the active metal surfaces. We confirm previously reported spectroscopic observations that show plasma-generated surface nitrogen can be converted to NH 3 through surface catalyzed pathways. Further, we demonstrate that the ammonia desorption peak temperature is sensitive to metal, with Pt desorbing NH 3 at the lowest temperature. Unsteady state microkinetic models of desorption kinetics as a function of initial N coverage and metal recover observed trends in NH 3 desorption temperatures and confirm that observed results reflect hydrogenation of plasma-induced N accommodation at each surface. In total, we show that the hydrogenation ability of the catalyst after plasma activation of N 2 is responsible for the reactivity trends observed in plasma-assisted NH 3 synthesis.
Decoding reactive structures in dilute alloy catalysts
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