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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.

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At least 919 records · Page 51
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Understanding the Origin of Negative Temperature Dependence and Activity of N-Coordinated Cobalt Sites During Ethylene Dimerization

The on-demand production of short-chain linear alpha olefins (LAOs; C4-C8) via C2H4 dimerization and oligomerization is industrially attractive, prompting extensive research on designing active, selective, and stable catalysts for industrial use. Cobalt supported on ammoniated carbon (Co(NH3)x/C) catalysts have shown remarkable activity and selectivity in this process. However, critical aspects such as the active phase, active site structure, the role of the catalyst support, cobalt loading effects, and the inverse correlation of the reaction rate with temperature remain inadequately understood. This study systematically explores these factors using a combination of steady-state differential catalytic tests, in situ molecular characterization including diffuse reflectance UV-Vis (DR-UV-Vis), Infrared, and Raman spectroscopies, and ex situ X-ray diffraction (XRD) and high annular aberration-corrected dark field transmission electron microscopy (HAADF-STEM). Various supports (SiO2, Al2O3, NH4-ZSM-5, g-C3N4, and C) and cobalt loadings (1.0-3.0 Co nm-2) were studied to determine the optimal catalyst composition and identify the active phase and sites. Carbon-supported catalysts uniquely produce C4-8 LAOs during C2H4 dimerization, with site-time-yield remaining constant (~10-3 s-1) for 1.0-4.0 Co nm-2 at prolonged reaction times (24-48?h time-on-stream). At higher loadings of 6.0 Co nm-2, the formation of crystalline CoO and Co3O4 phases reduces catalytic activity and LAO selectivity. Our findings show that active catalysts lack crystalline cobalt oxides and instead feature dispersed Co2+ sites, tetra-coordinated to a mix of N/NH3 and O/H2O ligands, which catalyze C2H4 dimerization via the Cossee-Arlman mechanism, exhibiting 1st order dependence on C2H4 concentration. The observed inverse rate-temperature correlation is attributed to compensation effects (i.e., presence of Cremer-Constable relationship) linked to changes in adsorption enthalpic and entropic factors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1988

A two-dimensional numerical simulation of a supersonic, chemically reacting mixing layer

Research has been undertaken to achieve an improved understanding of physical phenomena present when a supersonic flow undergoes chemical reaction. A detailed understanding of supersonic reacting flows is necessary to successfully develop advanced propulsion systems now planned for use late in this century and beyond. In order to explore such flows, a study was begun to create appropriate physical models for describing supersonic combustion, and to develop accurate and efficient numerical techniques for solving the governing equations that result from these models. From this work, two computer programs were written to study reacting flows. Both programs were constructed to consider the multicomponent diffusion and convection of important chemical species, the finite rate reaction of these species, and the resulting interaction of the fluid mechanics and the chemistry. The first program employed a finite difference scheme for integrating the governing equations, whereas the second used a hybrid Chebyshev pseudospectral technique for improved accuracy.

Drummond, J. Philip↗
DOE OSTI2021

Rapid Construction of Validated Chemistry Models for Advanced Biofuels (Co-Optima Final Report)

Computer methods were developed and demonstrated that make it possible to predict the combustion and pyrolysis chemistry of proposed biofuels, even before the biofuels are ever manufactured or experimentally tested. The methods are based on first-principles calculations of reaction rates and equilibria. A large number of complicated calculations are required, so we developed a computer workflow that automates many of the steps. With the chemical structure of the biofuel and the system conditions (temperature, pressure, compositions, etc.) as the input, the computer methods can construct a detailed kinetic model with refined parameters without intense human intervention. The automation of model construction makes it practical for a single engineer to make the predictions in a reasonable time period. The accuracy of the computer predictions was tested by measuring the time-profiles of various reaction intermediates (carbon monoxide, carbon dioxide, water, formaldehyde, methane, and ethylene) formed as the biofuels pyrolyze or ignite using sophisticated laser shock tube methods. Several biofuels, including methyl propyl ether, cyclopentanone, butyl acetate isomers, etc., were carefully studied to demonstrate the validity of the proposed computational and experimental methodology. This research project opens up the possibility for assessing some proposed biofuels on the computer without expensive experimental campaigns. The new computer methods are open source and well-documented, allowing a knowledgeable modeler to easily access the developed methods and implement them in their work routine. Moreover, they are also convenient and powerful, promising for developing the fuel chemistry models needed for use in engine simulators, facilitating co-optimization of new engine designs with new fuels.

09 BIOMASS FUELS↗
DOE OSTI2022

Multitask Machine Learning of Collective Variables for Enhanced Sampling of Rare Events

Computing accurate reaction rates is a central challenge in computational chemistry and biology because of the high cost of free energy estimation with unbiased molecular dynamics. In this work, a data-driven machine learning algorithm is devised to learn collective variables with a multitask neural network, where a common upstream part reduces the high dimensionality of atomic configurations to a low dimensional latent space and separate downstream parts map the latent space to predictions of basin class labels and potential energies. Here, the resulting latent space is shown to be an effective low-dimensional representation, capturing the reaction progress and guiding effective umbrella sampling to obtain accurate free energy landscapes. This approach is successfully applied to model systems including a 5D Müller Brown model, a 5D three-well model, the alanine dipeptide in vacuum, and an Au(110) surface reconstruction unit reaction. It enables automated dimensionality reduction for energy controlled reactions in complex systems, offers a unified and data-efficient framework that can be trained with limited data, and outperforms single-task learning approaches, including autoencoders.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

River Dynamics Control Transit Time Distributions and Biogeochemical Reactions in a Dam-Regulated River Corridor

Residence Time Distributions (RTDs) exert an important control on biogeochemical translation in the hydrological systems. Previous tracer studies have revealed that RTDs often followed time-invariant exponential, lognormal, or heavy-tailed RTDs that have power-law behavior for long tails in headwater or low-order streams. However, there is a recognition that RTDs can be more complicated and time-variable in response to dynamic hydrological forcing. Here, we use particle tracking to estimate RTDs along the Hanford Reach of the Columbia River and to quantify the influences of river stage fluctuations. Particle tracking is conducted using the velocity field from high-resolution 3D groundwater flow simulations. The effects of hydrological forcing on the residence time distribution were evaluated by varying river flow boundary conditions and releasing particles in different time windows. Our results revealed that dynamic stage fluctuations created rapidly changing losing-gaining conditions in the river and led to highly transient RTDs, which contributes to multiple modes of RTDs. Dam-induced high-frequency (sub-daily) flow variation contributes to the short-time (sub-daily) component of the RTDs. Deviation of the reactant consumption under the single-mode assumption compared to the multimodal RTDs is relatively small (~5%) and appears when the Damköhler number was close to one.More specifically, high-frequency (daily) dam-induced stage variations have higher impacts on biogeochemical reactions with faster reaction rate, and can potentially increase the reactant consumption by 26.68%. Based on these findings, we suggest that current river basin models could be improved by including bank storage and more complex RTDs influenced by both short and long term river stage fluctuations.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Revealing the Predominant Surface Facets of Rough Cu Electrodes under Electrochemical Conditions

Metal electrodes with rough surfaces are frequently found to convert CO or CO 2 to hydrocarbons and oxygenates with high selectivity and at high reaction rates in comparison with their smooth counterparts. The atomic-level morphology of a rough electrode is likely one key factor responsible for its comparatively high catalytic selectivity and activity. However, few methods are capable of probing the atomic-level structure of rough metal electrodes under electrocatalytic conditions. As a result, the nuances in the atomic-level surface morphology that control the catalytic characteristics of these electrodes have remained largely unexplored. Because the C≡O stretching frequency of atop-bound CO (CO atop ) depends on the coordination of the underlying metal atom, the IR spectrum of this reaction intermediate on the copper electrode could, in principle, provide structural information about the catalytic surface during electrolysis. However, other effects, such as dynamic dipole coupling, easily obscure the dependence of the frequency on the surface morphology. Further, in the limit of low CO atop coverage, where coupling effects are small, the C≡O stretching frequencies of CO atop on Cu(111) and Cu(100) facets are virtually identical. Therefore, on the basis of the C≡O stretching frequency, it is not straightforward to distinguish between these two ubiquitous surface facets, which exhibit vastly different CO reduction activities. Herein, we show that key features of the atomic-level surface morphology of rough copper electrodes can be inferred from the potential dependence of the line shape of the C≡O stretching band of CO atop . Specifically, we compared two types of rough copper thin-film electrodes that are routinely employed in the context of surface-enhanced infrared absorption spectroscopy (SEIRAS). We found that copper films that are electrochemically deposited on Si-supported Au films (CuAu–Si) are poor catalysts for the reduction of CO to ethylene in comparison to copper films (Cu–Si) that are electrolessly deposited onto Si crystals. As quantified by differential electrochemical mass spectrometry (DEMS), the onset potential for ethylene is ~200 ± 65 mV more cathodic for CuAu–Si than that for Cu–Si. To reveal the origin of the disparate catalytic properties of Cu–Si and CuAu–Si, we probed the surfaces of the electrodes with cyclic voltammetry (CV) and SEIRAS. The CV characterization suggests that the (111) surface facet predominates on CuAu–Si, whereas the (100) facet is more common on Cu–Si. SEIRAS reveals that the line shape of the C≡O stretching of CO atop is composed of two bands that are attributable to CO atop on terrace and defect sites. The different surface structures manifest themselves in the form of starkly different potential dependences of the line shape of the C≡O stretching mode of CO atop on the two types of electrodes. With a simple Boltzmann model that considers the different adsorption energies of CO atop on terrace and defect sites, and the resulting CO atop populations on terrace and defect sites, we deduced that the observed electrode-specific potential dependence of the line shape is consistent with the presence of different predominant terrace sites on the two types of films. This strategy for assessing the atomic-level morphology is not restricted to SEIRAS but could also be applied to the C≡O stretching bands recorded with surface-enhanced Raman spectroscopy (SERS), which is suitable for probing a wide range of rough copper electrodes. Therefore, with this work, we establish the potential dependence of the C≡O stretching band of CO atop as a probe of the atomic-level surface structure of rough metal electrodes under electrochemical conditions. When it is coupled with complementary techniques, this methodology provides essential structural information for further improvement in the reaction selectivity of rough metal electrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2014

Calculation of State Specific Rate Coefficients for Non-Equilibrium Hypersonics Applications: from H(Psi) = E(Psi) to k(T) = A *exp(-E(sub a)/RT)

Development of High-Fidelity Physics-Based Models to describe hypersonic flight through the atmospheres of Earth and Mars is underway at NASA Ames Research Center. The goal is to construct chemistry models of the collisional and radiative processes that occur in the bow shock and boundary layers of spacecraft during atmospheric entry that are free of empiricism. In this talk I will discuss our philosophy and describe some of our progress. Topics to be covered include thermochemistry, internal energy relaxation, collisional dissociation and radiative emission and absorption. For this work we start by solving the Schrodinger equation to obtain accurate interaction potentials and radiative properties. Then we invoke classical mechanics to compute state-specific heavy particle collision cross sections and reaction rate coefficients. Finally, phenomenological rate coefficients and relaxation times are determined from master equation solutions.

aerothermodynamics↗
DOE OSTI2024

Assessment of Long-Term Degradation of Adsorbents for Direct Air Capture by Ozonolysis

Porous adsorbents are a promising class of materials for the direct air capture of CO 2 (DAC). Practical implementation of adsorption-based DAC requires adsorbents that can be used for thousands of adsorption–desorption cycles without significant degradation. We examined the potential degradation of adsorbents by a mechanism that appears to have not been considered previously, namely, ozonolysis by trace levels of ozone from ambient air. We focused on amine-appended metal–organic frameworks, specifically amine-functionalized Mg 2 (dobpdc), as a representative DAC adsorbent. Estimates based on the number of amine sites in these adsorbents and the ozone concentration in air suggest that degradation by ozone may be relevant over thousands of adsorption–desorption cycles if reactions with adsorbed ozone are fast. We used density functional theory calculations to estimate reaction rates for amine groups and carbon–carbon double bonds in amine-functionalized Mg 2 (dobpdc).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Cross-section measurements to low-lying excited final states in the 24 M(α,p) 27 Al*(γ) reaction as an energy source for x-ray bursts

Energy production in Type Ia x-ray bursts depends on a number of nuclear reactions that become efficient in a hot environment (up to 2 GK). Model sensitivity studies have been performed in an effort to better identify the reactions that have the largest effect, but these efforts are hampered by the high level of complexity of the astrophysical model and large nuclear physics uncertainties. In a recent study, the 24 Mg(α,p) 27 Al reaction was found to significantly affect the energy generation in x-ray bursts. This manuscript reports the first study of the 24 Mg(α,p 1,2 γ) 27 Al reaction at energies relevant for x-ray bursts. In conclusion, the branches to the 27 Al excited states increase to a small degree the estimates of the total astrophysical 24 Mg(α,p) 27 Al reaction rate.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Hybrid Density Functional Theory Comparison of Oxygen Release and Solvent Decomposition Kinetics on Li x NiO 2 Surfaces

High-nickel-content layered oxides are among the most promising electric vehicle battery cathode materials. However, their interfacial reactivity with electrolytes and tendency toward oxygen release (possibly yielding reactive 1 O 2 ) remain degradation concerns. Elucidating the most relevant (i.e., fastest) interfacial degradation mechanism will facilitate future mitigation strategies. We apply screened hybrid density functional (HSE06) calculations to compare the reaction kinetics of Li x NiO 2 surfaces with ethylene carbonate (EC) with those of O 2 release. Further, on both the (001) and (104) facets, EC oxidative decomposition exhibits lower activation energies than O 2 release. Our calculations, coupled with previously computed liquid-phase reaction rates of 1 O 2 with EC, strongly question the role of “reactive 1 O 2 ” species in electrolyte oxidative degradation. The possible role of other oxygen species is discussed. To deal with the challenges of modeling Li x NiO 2 surface reactivity, we emphasize a “local structure” approach instead of pursuing the global energy minimum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The rate of development of atomic mixing and temperature equilibration in inertial confinement fusion implosions

The MARBLE project is a novel inertial confinement fusion platform for studying the development of atomic mixing and temperature equilibration in inertial confinement fusion implosions and their impact on thermonuclear burn. Experiments involve the laser-driven implosion of capsules filled with deuterated engineered foams whose pores are filled with a gaseous mixture of hydrogen and tritium. By varying the size of the foam pores, we can study the timescale of the development of atomic mix relative to the development of thermal equilibrium between species. In contrast, previous separated reactant experiments have only provided information on the total amount of mix mass. Additionally, we report on the series of MARBLE experiments [first reported in Haines et al., Nat. Commun. 11, 544 (2020)] performed on the University of Rochester's OMEGA laser facility and detailed and highly resolved three-dimensional radiation-hydrodynamic simulations of the implosions. In both the experimental and simulation results, we observe that the reactants do not achieve thermal equilibrium during the course of the implosion except in atomically mixed regions—i.e., that atomic mixing develops faster than thermal equilibration between species. The results suggest that ion temperature variations in the mixture are at least as important as reactant concentration variations for determining the fusion reaction rates.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Synthesis and Characterization of Pd-based Nanomaterials

Bimetallic nanoparticles (BNPs) consist of two different types of metals or alloys that are bonded together. Unique properties such as optical, electronic, thermal, and catalytic effects differ for each type of BNP. Important BNPs range from Au-Pd, Ag- Pt, Au-Pt, and Ag-Ni. Pd bimetallic nanoparticles are of interest due to their many applications such as catalysis and sensing. Bimetallic catalysts have increase reaction rates and have improved catalyst stability through the geometry and ligand distribution. Pd nanoparticles are considered to be a strong catalyst due to their high activity at low temperatures and high tolerance to moisture. The catalytic properties of bimetallic nanoparticles depend on the structural properties such as size and shape. Core-shell, hollow structure, and multi-shell alloy are three possible structures nanoparticles can form as bimetallic catalysts. BNPs can be synthesized through different methods to control the size, shape, and structure. To obtain different morphologies, a variety of methods can be performed. Different methods can range from the usage of the glancing angle deposition (GLAD) to the galvanic replacement reaction, but the methods all depend on the properties of the metals. The galvanic displacement reaction was the method used to obtain Pd-based nanoparticles. This reaction is best know for obtaining hollow shaped NPs. To determine what redox process was preformed, the activity series of metals was used. From the activity series of metals, silver (Ag) was selected to preform Pd-based nanoparticles. Objectives: Synthesize Ag nanoparticles and Ag-Pd nanoparticles to understand the morphology. Characterize the synthesized nanoparticles using scanning electron microscopy (SEM), phase analysis light scattering (PALS), dynamic light scattering (DLS), energy dispersive X-ray spectroscopy (EDS), and UV-Vis spectroscopy. Results: In the UV-Vis spectrum, the Ag-Pd bimetallic NP's plasmon band decreased as the volume of palladium increased. The surface charge increases as the concentration of palladium increases. The Pd{sup 2+} ions interact with the sodium citrate surface, and decrease the negative charge. Conclusion: Ag-Pd nanoparticles were successfully created and stabilized with sodium citrate. The addition of Pd decreased the prominent plasmon band of the Ag nanoparticles. The SEM analysis showed that Ag nanoparticles had a well-defined structure, while the Ag-Pd nanoparticles showed hollow and rough structure. The EDX analysis confirmed the presence of silver and palladium. This material can be used in many industrial and research fields such as organic synthesis, fuel cells, and environmental sensing and remediation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Reaction–drift–diffusion models from master equations: application to material defects

We present a general method to produce well-conditioned continuum reaction–drift–diffusion equations directly from master equations on a discrete, periodic state space. We assume the underlying data to be kinetic Monte Carlo models (i.e. continuous-time Markov chains) produced from atomic sampling of point defects in locally periodic environments, such as perfect lattices, ordered surface structures or dislocation cores, possibly under the influence of a slowly varying external field. Our approach also applies to any discrete, periodic Markov chain. Here, the analysis identifies a previously omitted non-equilibrium drift term, present even in the absence of external forces, which can compete in magnitude with the reaction rates, thus being essential to correctly capture the kinetics. To remove fast modes which hinder time integration, we use a generalized Bloch relation to efficiently calculate the eigenspectrum of the master equation. A well conditioned continuum equation then emerges by searching for spectral gaps in the long wavelength limit, using an established kinetic clustering algorithm to define a proper reduced, Markovian state space.

36 MATERIALS SCIENCE↗
DOE OSTI2025

The use of D–D reactions to diagnose the lifetime of spin polarized fuel

If the nuclei remain polarized, spin polarized fuel can increase the fusion power produced in a reactor while using less fuel. This study assesses whether reactions between an unpolarized deuterium (D) beam and polarized deuterium nuclei can in principle experimentally ascertain the persistence of nuclear polarization in a magnetic fusion experiment. The differential cross section for D–D reactions between unpolarized and polarized nuclei depends upon polarization, so the polarization state can be inferred from measurements of the D–D fusion products. An evaluation is performed for 3 MeV proton detection in the DIII-D tokamak using 81 keV neutral beams and polarized target fuel injected as a pellet. Measurement of the escaping proton pitch v 3 ∥ v 3 is insensitive to the degree of polarization but energy-resolved measurements are sensitive. The sensitivity is comparable for different angles of beam injection. Because the D–D reaction rate is large for this scenario, uncertainties associated with counting statistics are small, making inference of the polarization feasible with current technology.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Non-adiabatic quantum interference in the ultracold Li + LiNa → Li 2 + Na reaction

Electronically non-adiabatic effects play an important role in many chemical reactions. However, how these effects manifest in cold and ultracold chemistry remains largely unexplored. Here for the first time we present from first principles the non-adiabatic quantum dynamics of the reactive scattering between ultracold alkali-metal LiNa molecules and Li atoms. We show that non-adiabatic dynamics induces quantum interference effects that dramatically alter the ultracold rotationally resolved reaction rate coefficients. The interference effect arises from the conical intersection between the ground and an excited electronic state that is energetically accessible even for ultracold collisions. These unique interference effects might be exploited for quantum control applications such as a quantum molecular switch. The non-adiabatic dynamics are based on full-dimensional ab initio potential energy surfaces for the two electronic states that includes the non-adiabatic couplings and an accurate treatment of the long-range interactions. A statistical analysis of rotational populations of the Li2 product reveals a Poisson distribution implying the underlying classical dynamics are chaotic. The Poisson distribution is robust and amenable to experimental verification and appears to be a universal property of ultracold reactions involving alkali metal dimers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Six-coordinate ruthenium water oxidation catalysts bearing equatorial polypyridinedicarboxylato and axial phosphine ligands

Ruthenium catalysts for water oxidation combining multidentate ligands [2,2':6',2"-terpyridine]-6,6"-dicarboxylato (tda) and 2,2'-bipyridine-6,6'-dicarboxylato (bda) with apical phosphine ligands have been prepared. Here, these new complexes were fully characterized by standard spectroscopic and single-crystal X-ray crystallography analyses, and their redox properties were evaluated by electrochemistry. Specifically, [Ru II (tda)(tris(2-furyl)phosphine) 2 ] displayed two reversible redox waves that were assigned to the Ru II/III and Ru III/IV transitions, respectively. The number of turnovers in Ce IV -driven water oxidation reached 258 for the bda analog, and for the tda analog, early reaction rates were first order in initial catalyst concentration. The effects of adding fractional equivalents of Ce IV were studied using UV–vis spectroscopy. Steric and electronic changes in the axial phosphine ligand can exert their effects on the properties and catalytic activity of the resulting complexes, which may be useful when exploring other chemistry of these complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Low-energy cross-section measurement of the B 10 ( α , n ) N 13 reaction and its impact on neutron production in first-generation stars

Nucleosynthesis in the first generation of massive stars offers a unique setting to explore the creation of the first heavier nuclei in an environment free of impurities from earlier stellar generations. In later generations of massive stars, hydrogen burning occurs predominantly through the CNO cycles, but without the carbon, nitrogen, and oxygen to catalyze the reaction sequence, first stars would have to rely on the inefficient pp chains for their energy production. Observations of second and third generation stars show pronounced abundances of carbon and oxygen isotopes, which suggests a rapid conversion of the primordial abundances to heavier elements. While the triple-alpha-process primarily facilitates this conversion, there are alternative reaction sequences, such as 2 H(α,γ) 6 Li(α,γ) 10 B(α,n) 13 N, that may play a significant role. To study such alternate reaction pathways for production of carbon and heavier nuclei, a number of new measurements are needed. In this work, new measurements are reported for the 10 B(α,n) 13 N reaction, extending the cross section down to 575 keV incident α-particle energy. The measurements were made using a state-of-the-art deuterated liquid scintillator and a spectrum unfolding technique. An R-matrix analysis was performed in order to facilitate a comparison of the underlying nuclear structure with the reaction measurements. An unexpected upturn is observed in the low-energy S factor that indicates the presence of a new low-energy resonance. Finally, a revised reaction rate is determined that takes into account the present data as well as other previous measurements from the literature that were previously neglected.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Physics-based, neural network force fields for reactive molecular dynamics: Investigation of carbene formation from [EMIM + ][OAc - ]

Reactive molecular dynamics simulations enable detailed understanding of solvent effects on chemical reaction mechanisms and reaction rates. While classical molecular dynamics using reactive force fields allows significantly longer simulation time scales and larger system sizes compared with ab initio molecular dynamics, constructing reactive force fields is a difficult and complex task. In this work, we describe a general approach following the Empirical Valence Bond (EVB) framework for constructing ab initio reactive force fields for condensed phase simulations by combining physics-based methods with neural networks (PB/NN). The physics-based terms ensure correct asymptotic behavior of electrostatic, polarization, and dispersion interactions, and are compatible with existing solvent force fields. Neural networks are utilized for versatile description of short-range orbital interactions within the transition state region, and accurate rendering of vibrational motion of the reacting complex. Herein, we demonstrate our methodology for a simple deprotonation reaction of the 1-ethyl-3-methylimidazolium (EMIM+) cation with acetate to form 1-ethyl- 3-methylimidazol-2-ylidene and acetic acid. Our PB/NN force field exhibits ~ 1 kJ/mol MAE accuracy within the transition state region for the gas-phase complex. To characterize solvent modulation of the reaction profile, we compute potentials of mean force (PMFs) for the gas-phase reaction as well as the reaction within a four ion cluster, and benchmark against ab initio molecular dynamics simulations. We find that the surrounding ionic environment significantly destabilizes formation of the carbene product, and we show that this effect is accurately captured by the reactive force field. By construction, the PB/NN potential may be directly employed for simulations of other solvents/chemical environments without additional parameterization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗