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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Computational Investigations of the Reactivity of Metalloporphyrins for Ammonia Oxidation

Density functional theory and molecular dynamics simulations were used to assess the ability of tetraphenylporphyrin (TPP)M complexes (where M = Cr, Mn, Fe, Co, Ni, Mo, Ru, W, and Os) to coordinate and weaken the N-H bonds of ammonia, as well as their reactivity towards N-N bond formation for N 2 generation. Compared to other metalloporphyrins, bis-ammonia complexes (TPP)Mo(NH 3 ) 2 and (TPP)W(NH 3 ) 2 exhibit low and level N-H BDFEs due to a stabilized (TPP)M(NH 3 )(NH) intermediate by multiple metal-ligand bonding. These results resemble those previously obtained for polypyridyl metal complexes, suggesting that broad trends in reactivity towards N-H bond cleavage are more metal-dependent rather than ligand-dependent for a metal in a nitrogen pseudo-octahedral environment. We investigated N-N bond formation via NH 3 nucleophilic attack on M-NH and M-N intermediates, compared to bimolecular coupling of M-NH x intermediates. We evaluated the reactivity of (TPP)Fe(NH 3 ) 2 towards N-N bond formation via a hydrazine pathway, and found amide-amide coupling to form a bridged hydrazido complex to be the most favorable pathway for N-N bond formation. Further investigation of possible N-N bond formation pathways by reaction with NH 3 led us to identify a possible Fe III -•NH species with significant aminyl character that bypasses the nucleophilic attack of NH 3 and that promotes homolytic N-H bond cleavage of ammonia. This reaction forms a Fe-NH 2 moiety and a transient •NH 2 radical that subsequently forms an N-N bond with the Fe-NH 2 moiety to form a (TPP)Fe(NH 3 )(N 2 H 4 ) species. Furthermore, these results indicate the need to evaluate the radical character of imido species and their reactivity towards N-H bond cleavage of ammonia.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Corrosion Behavior of a Reactive Bond Between Stainless Steel and a Cast AlCeMg Alloy

Corrosion is a longstanding issue for metal components, especially those used in heat exchanger applications. Al–Ce–Mg alloys may provide a potential solution to this problem due to their good mechanical properties and potential reaction bonding with other metals. The reaction bonding involves a “reactive” bond that occurs upon casting of Al–Ce–Mg alloy over stainless steel (SS). Here this study examined the corrosion response of Al–2Ce–6Mg (atomic percent)/(SS) reactive bond interfaces after samples were completely submerged in nitric, sulfuric, formic, and mixed acids for 267 h. Scanning electron microscopy revealed that in the as-cut condition, reactive bond formations were seen frequently throughout the length of the casting and maintained a secure bond between the alloy and the SS tubes. Furthermore, the nitric, sulfuric, and the mixed acids did not have a deleterious effect on the reactive bond structure. However, formic acid did produce changes in both the microstructural appearance and the elemental profile across the bond due to the formation of corrosion reaction products on the acid-exposed surface.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Lie group analysis of the point-reactor neutron kinetics equations for various reactivity models

This work applies Lie Group Theory to the nonlinear point-reactor neutron kinetics equations for several reactivity feedback and reactivity insertion models. The goal of this work is to connect known analytical solutions to their corresponding Lie groups as well as to obtain new analytical solutions and the circumstances from which they arise. The reactivity models we consider are the Nordheim-Fuchs Model, an arbitrary-order polynomial reactivity insertion model, and the Fuchs Ramp-Insertion Model. In all three models, we generalize the analysis when possible and obtain analytical solutions in every case. For the first two models, we succeed in finding the Lie groups corresponding to classical solutions and find additional solutions that were otherwise unknown. Finally, for the final model, we obtain a reduced-order nonlinear kinetics equation which is not analytically solvable, but by applying a second-order truncation, we find a novel closed-form solution and demonstrate its validity with a numerical example.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

Combining direct ink writing with reactive melt infiltration to create architectured thermoelectric legs

Here, we present a new additive-reactive synthesis method where inks – cast into molds or 3D-additively extruded into architectured shapes – are reacted into intermetallic thermoelectric compounds. The new method, as demonstrated for equiatomic TiNiSn, combines: (i) extrusion printing (or casting) of inks containing Ni and Ti powders, (ii) debinding and reactive sintering to form a porous NiTi network, (iii) network infiltration with liquid Sn and subsequent reaction to synthesize the TiNiSn phase. Thin plates, created through this method, show high phase purity and low residual porosity. A thermoelectric figure of merit zT = 0.47 ± 0.05 is achieved at 800 K, within the broad range of values (zT= 0.3–1.0) reported for TiNiSn created via traditional powder hot-pressing methods. Layered TiNiSn microlattices – after 3D ink-extrusion printing and infiltration – exhibit high relative densities and minimal undesirable secondary phase content, with a Seebeck coefficient on par with the ink-cast TiNiSn plates, demonstrating that thermoelectric legs with far-ranging architectural freedom can be created additively with this novel reactive manufacturing method. Numerous other thermoelectric (and other) compounds, currently limited to basic geometries due to brittleness, are amenable to this new method based on a sequence of reactive sintering/infiltration of cast or ink-extruded precursors.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Intrinsic reactivity and dissolution characteristics of tetracalcium aluminoferrite

Tetracalcium aluminoferrite is one of the main phases of Portland cement, the dissolution characteristics of which however have not been fully revealed. This work adopted first-principles calculations and Mössbauer spectroscopy as well as X-ray diffraction analysis to clarify the intrinsic reactivity of different species of tetracalcium aluminoferrite crystals. Ca ions are the most reactive species of tetracalcium aluminoferrite and Al ions are slightly more reactive than Fe ions. Moreover, the tetrahedral Al and Fe ions are more reactive than the octahedral Al and Fe ions. These indicate dissolution characteristics of tetracalcium aluminoferrite crystals, namely, Ca ions dissolve first and the tetrahedral species dissolve faster than the octahedral species. After the initial dissolution, the dissolved ions nucleate and grow on the defective surface of C{sub 4}AF and the C{sub 4}AF residues are fully hydroxylated. The further hydration thereafter becomes the complex dissolution with the nucleation and growth of hydration products.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Mechanochemical synthesis of hydraulically reactive calcium silicate minerals via thermally-assisted mechanical grinding

This study explores a thermally assisted mechanochemical approach alternative to conventional cement synthesis as a potential to produce hydraulically reactive calcium silicate phases. Ball milling of mixed CaO/SiO 2 feedstocks at temperature ranges 100-300 °C increases the formation of the Ca-O-Si bonds and precursor reactivity. Spectroscopic analyses (FTIR, MAS-NMR, UV-Vis DRS) indicate increasing amorphization with milling temperature, attributed to improved mixing and thermally assisted diffusion. Upon hydration, all treated samples exhibit exothermic heat release, with the sample prepared at 300 °C showing the most pronounced reactivity. Thermal analysis reveals weight loss consistent with C-S-H formation, confirming cement-like behavior. In summary, moderate thermal input during milling promotes structural activation and enhances downstream hydraulic reactivity, providing a proof-of-concept for energy-reduced cement precursor processing.

Alite↗
DOE OSTI2023

Pressure effects on reactivity and extinction of n -dodecane diffusion cool flame

Low-temperature combustion at high pressure has gained increasing interest owing to the growing demand for clean and efficient propulsion and energy systems. In particular, cool flame structure, extinction limits, and fuel reactivities at high pressure are critical in affecting the engine performance at near-limit conditions. Here, this paper investigates the effects of pressure on the cool flame extinction limit, structure, radical index, reactivity, and oxygen concentration dependence by experiments, analysis, and modeling. A large n-alkane, namely n-dodecane (n C 12 H 26 ), is selected to study its diffusion cool flame dynamics and reactivity in a high-pressure counterflow burner up to 10 atm. The experimental results show that higher pressure increases the cool flame extinction strain rates, and that the pressure-weighted extinction strain rate (aP) is proportional to the square of pressure, P 2 . A scaling analysis explains the relationship between the dependence of flame structure, heat release rate, and pressure-weighted cool flame strain rate on pressure. Furthermore, radical indexes at different pressures are measured by isolating the thermal and transport effects from the chemical contribution to diffusion cool flame extinction. The radical index clearly shows that the low-temperature reactivity increases with pressure. In addition, due to the critical role of multiple oxygen addition reactions in low-temperature chemistry, the relationship between the cool flame extinction limit and the oxygen concentration is explored. It is found that the cool flame extinction limits are proportional to the n th power of the oxygen concentration, [O 2 ] n , and increasing pressure leads to stronger extinction limit dependence (larger n) on the oxygen concentration. The present experiment and detailed kinetic analysis show clearly that increasing pressure promotes the low-temperature chemistry including the oxygen addition reactions, while the scaling analysis explains well the experimental results.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2020

Sulfuric Acid Improves the Reactivity of Zeolites via Dealumination

The demand for supplementary cementitious materials (SCMs), like fly ash, slag, and silica fume, is projected to rise over the next few decades. However, global decarbonization efforts, such as decommissioning of coal-fired power plants, will limit the supply of SCMs. Therefore, alternative SCM sources are a critical need for the cement and concrete industry. However, the high crystallinity of zeolites limits their pozzolanic reactivity. The goal of this work was to improve the reactivity of two common zeolites, namely clinoptilolite and SSZ-13, by treating them with sulfuric acid. The treatment enhanced zeolite reactivity via dealumination and decreased particle sizes, which led to increased reactivity with calcium hydroxide, as indicated by a 42.0% increase in reaction heat measured by isothermal calorimetry. Here, we elucidate mechanistic understanding that smaller particle sizes induced by acid treatment accelerated peak heat evolution, while free aluminates from dealumination increased heat via direct reaction with aqueous Ca 2+ .

36 MATERIALS SCIENCE↗
DOE OSTI2019

Single-fuel reactivity controlled compression ignition through catalytic partial oxidation reformation of diesel fuel

A single-fuel RCCI concept has been proposed to avoid the need for a secondary fuel system required for conventional RCCI by generating the secondary fuel from the primary fuel through catalytic partial oxidation (CPOX) reformation. In conventional RCCI, gasoline or natural gas can be used as the low-reactivity fuel, and diesel can be used as the high-reactivity fuel. In this study, two reformate mixtures generated by reforming diesel fuel at different operating conditions were used as the low-reactivity fuel, with the parent diesel as the high reactivity fuel. The combustion characteristics of reformate-diesel RCCI were compared with the conventional RCCI. A CFD model was also developed and validated against the experimental results. The model was then used to validate a necessary approximation of the reformate mixture's species concentrations. Compared to conventional RCCI fuel pairs, reformate-diesel RCCI shows marginally better thermal efficiency, approximately 10% better THC emissions, approximately 50% lower NOx emissions, and good controllability. Because the reformate mixture has a high concentration of diluents it displaces a large fraction of intake air and acts similarly to EGR. The combustion behavior of reformate-diesel RCCI is in between that of gasoline-diesel and natural gas-diesel conventional RCCI. From the results, it can be concluded that reformate-diesel RCCI is not overly sensitive to the reformation process itself and the exact species concentrations in the reformate mixture. Finally, a small change in the start of injection of diesel, blend ratio, and EGR fraction can be used to compensate for reformate mixture concentration differences.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2024

Combustion characteristics of diisopropoxymethane, a low-reactivity oxymethylene ether

Oxymethylene ethers (OMEs) have been studied for use as low-sooting diesel fuel additives or substitutes; very little literature discusses OMEs as spark-ignition (SI) fuels due to their typically high cetane numbers. In this work, a lower-reactivity, branched OME, diisopropoxymethane (DIPM), is evaluated to determine its effectiveness as a spark-ignition fuel, as it is the lowest-reactivity OME (as determined by Indicated Cetane Number) thus far evaluated in the literature. DIPM is synthesized in-house via acetalization from isopropanol (iPrOH) and trioxane using standard OME production practices. DIPM was then tested in a rapid compression machine (RCM) for autoignition and spark ignition characteristics, and in a modified CFR engine to determine effective octane numbers. In the RCM, an autoignition temperature sweep was performed at stoichiometric conditions from 1000/T = 1.7 - 1.0, at 5:1 inert ratio (comparable to approximately 25% EGR), where it was found that DIPM has ignition delay times 5–10x faster than isooctane and displays NTC ignition behavior. Blends with iPrOH indicate that reactivity can be matched with isooctane with low blend ratios of iPrOH in DIPM. Flame speeds were tested with a laser spark for ignition in the RCM, where the flame speed of DIPM and isooctane is determined to be comparable at engine relevant conditions. In the CFR engine, effective RON and MON based on pressure trace frequency domain measurements were determined for DIPM and a 15 vol% iPrOH in DIPM blend. Neat DIPM has (R+M)/2 = 59 and a negative sensitivity of S = -18, consistent with its NTC behavior and higher reactivity. Furthermore the DIPM/iPrOH blend has positive sensitivity and a pump-gasoline range (R+M)/2 = 89.3. DIPM on its own is unlikely to be an effective SI fuel, however, when blended with iPrOH as an ON booster, it may be a promising SI candidate fuel.

09 BIOMASS FUELS↗
DOE OSTI2020

W-ZrC composites prepared by reactive melt infiltration of Zr 2 Cu alloy into binder jet 3D printed WC preforms

W-ZrC composites were successfully prepared by reactive melt infiltration (RMI) of stoichiometric and excess amounts of Zr 2 Cu into sintered and un-sintered WC preforms made from binder jet 3D printing. The focus of this work was to study the conversion of reactant powders and liquid infiltrant with varying preform density and infiltrant amount by controlling the processing time to reach high conversion yield while understanding the phase composition, microstructure, and hardness. To investigate the effect of time, the reactive melt infiltration was conducted at 1400 °C for 2, 4 and 8 h in a furnace with 96% Ar - 4% H2 gas atmosphere. The increase in reaction time from 2 to 8 h increased the W and W 2 C phase contents and decreased the ZrC phase content when using sintered WC preforms. Samples prepared from un-sintered WC preforms exhibited improved reactive melt infiltration compared to sintered samples, and there was no detectable W 2 C phase and nearly full consumption of WC. Similar to sintered WC samples, the content of W and ZrC phases increased with the increase in time from 2 to 8 h. The interfaces and phases at reaction interfaces were investigated using electron diffraction analysis and S/TEM-EDS to understand material stability; the phases were identified and consistent with XRD analysis. Additionally, there was no Cu present at the interfaces. Increasing the amount of infiltrant led to better reactive melt infiltration. In general, the hardness increased with reaction time and the highest Vickers hardness was found in the W-ZrC sample formed from sintered WC reacted with excess Zr 2 Cu. Finally, this research addresses the critical comparison of sintering and RMI time and shows that by using un-sintered samples for 8 h we are able to achieve W-ZrC composites with fewer undesired phases.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Synthesis of bulk reactive Ni–Al composites using high pressure torsion

Self-propagating exothermic reactions, for instance in the nickel-aluminum (Ni-Al) system, have been widely studied to create high performance intermetallic compounds or for in-situ welding. Their easy ignition once the phase spacing is reduced below the micron scale, makes top-down methods like high-energy ball milling, ideal to fabricate such reactive nanostructures. A major drawback of ball milling is the need of a sintering step to form bulk pieces of the reactive material. However, this is not possible, as the targeted reactions would already proceed. Therefore, we investigate the ability of high pressure torsion as an alternative process, capable to produce bulk nanocomposites from powder mixtures. Severe straining of powder mixtures with a composition of 50 wt% Ni and 50 wt% Al enables fabrication of self-reactive bulk samples with microstructures similar to those obtained from ball milling or magnetron sputtering. Additionally, samples deformed at ambient temperature are highly reactive and can be ignited significantly below the Al melting point, finally predominantly consisting of Al 3 Ni 2 and Al 3 Ni, independent of the applied strain. Although the reaction proceeds first at the edge of the disk, the strain gradient present in the disks does not prevent reaction of the whole sample.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Local molecular environment drives speciation and reactivity of ion complexes in concentrated salt solution

The speciation and reactivity of aqueous salt solutions are important for a wide variety of applications. However, application of this information is inhibited by broad disagreement about composition, mechanisms, and structure in concentrated solutions especially. Here, neutron diffraction with isotopic substitution measurements on aqueous zinc chloride solutions are used to calibrate molecular dynamics simulations that include effective electronic polarization. This allows us to probe the origin of speciation and reactivity of zinc chloride-water ion complexes, ZnCl x (H 2 O) y 2-x (x ≤ 4 and y ≤ 6), by comparing the reactivity of species in concentrated (4.5 m) and dilute (0.01 m) conditions. Within the concentrated solution, it is found that the extended solvation environment is dominated by solvent-separated ion complexes whose presence increases the free energy of activation for interconversion of species while simultaneously enhancing their thermodynamic stability. This concentration-dependent reactivity and stability suggests that other reactions, such as the nucleation of solid phases, will also be affected.

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

A comparative reactivity study of 1-alkene fuels from ethylene to 1-heptene

In this work, a comparative reactivity study of 1-alkene fuels from ethylene to 1-heptene has been performed using ignition delay time (IDT) measurements from both a high-pressure shock tube and a rapid compression machine, at an equivalence ratio of 1.0 in ‘air’, at a pressure of 30 atm in the temperature range of 600–1300 K. At low temperatures (< 950 K), the results show that 1-alkenes with longer carbon chains show higher fuel reactivity, with 1-pentene being the first fuel to show negative temperature coefficient (NTC) behavior followed by 1-hexene and 1-heptene. At high temperatures (> 950 K), the experimental results show that all of the fuels except propene show very similar fuel reactivity, with the IDTs of propene being approximately four times longer than for all of the other 1-alkenes. To analyze the experimental results, a chemistry mechanism has been developed using consistent rate constants for these alkenes. At 650 K, flux analyses show that hydroxyl radicals add to the double bond, followed by addition to molecular oxygen producing hydroxy-alkylperoxy radicals, which can proceed via the Waddington mechanism or alternate internal H-atom isomerizations in chain branching similar to those for alkanes. We have found that the major chain propagation reaction pathways that compete with chain branching pathyways mainly produce hydroxyl rather than hydroperoxyl radicals, which explains the less pronounced NTC behavior for larger 1-alkenes compared to their corresponding alkanes. At 1200 K, flux analyses show that the accumulation of hydroperoxyl radicals is important for the auto-ignition of 1-alkenes from propene to 1-heptene. The rate of production of hydroperoxyl radicals for 1-alkenes from 1-butene to 1-heptene is higher than that for propene, which is due to the longer carbon chain facilitating hydroperoxyl radical formation via more efficient reaction pathways. This is the major reason that propene presents lower fuel reactivity than the other 1-alkenes at high temperatures.

1-Alkene↗
DOE OSTI2021

Reactivity of CO 2 with Utica, Marcellus, Barnett, and Eagle Ford Shales and Impact on Permeability

We report that in order to reduce greenhouse gas emissions while recovering hydrocarbons from unconventional shale formations, processes that make use of carbon dioxide to enhance oil recovery while storing carbon dioxide (CO 2 ) should be considered. Here, we examine samples from three shale basins across the United States (Utica and Marcellus Shales in the Appalachian Basin, Barnett Shale in the Bend Arch-Ft. Worth Basin, and Eagle Ford in the Western Gulf Basin) to address the following questions: (1) do changes from reaction with CO 2 and fluids at the micrometer and nanometer scale alter flow pathways and, in turn, impact hydrocarbon production, CO 2 storage, and seal integrity and (2) can CO 2 or fluid reactivity be predicted based on physical or chemical properties of shale formations? Experiments were conducted at 40 °C and 10.3 MPa to characterize the interaction between CO 2 and shale using X-ray diffraction (XRD), carbon and sulfur analysis, in situ Fourier transform infrared spectroscopy (FT-IR), feature relocation scanning electron microscopy coupled with energy-dispersive spectroscopy (SEM-EDS), mercury (Hg) intrusion porosimetry, and Brunauer-Emmett-Teller (BET) surface area and pore size analysis coupled with density functional theory (DFT) methods. Changes in mechanical, physical, and flow properties of shale cores due to CO 2 exposure were addressed using a New England Research Autolab 1500 and Xenon X-ray computed tomography (CT) scanning. Results showed that CO 2 did not promote significant reactivity with the shale if water was not present; only shales with swelling clays or residual interstitial pore water reacted with dry CO 2 to promote reactivity in shale. When water was added as a reactant, CO 2 formed carbonic acid and reacted with the shale to dissolve carbonate pockets, etched and pitted the shale matrix surfaces, and increased the microporosity and decreased nanoporosity. Porosity and permeability increased appreciably in core shale samples after exposure to CO 2 saturated fluid due to dissolution of carbonate. Shale mechanical properties were not altered. Trends were not observed that could tie CO 2 or fluid reactivity to physical or chemical properties of the shale formations at the basin scale from the samples we examined. However, if the shale contained significant amounts of carbonate and water was available to react with the CO 2 , pore sizes were altered in the matrix and permeability and porosity increased.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2022

Effect of Redox-Inactive Metal Ion–Nickel(III) Interactions on the Redox Properties and Proton-Coupled Electron Transfer Reactivity

We report Mononuclear nickel(II) and nickel(III) complexes of a bisamidate-bisalkoxide ligand, (NMe 4 ) 2 [Ni- II (HMPAB)] (1) and (NMe 4 )[Ni III (HMPAB)] (2), respectively, have been synthesized and characterized by various spectroscopic techniques including X-ray crystallography. The reaction of redox-inactive metal ions (M n+ = Ca 2+ , Mg 2+ , Zn 2+ , Y 3+ , and Sc 3+ ) with 2 resulted in 2-M n+ adducts, which was assessed by an array of spectroscopic techniques including X-ray absorption spectroscopy (XAS), electron paramagnetic resonance (EPR), and reactivity studies. The X-ray structure of Ca 2+ coordinated to Ni(III) complexes, 2Ca 2+ T, was determined and exhibited an average Ni-Ca distance of 3.1253 angstrom, close to the metal ions' covalent radius. XAS analysis of 2-Ca 2+ and 2-Y 3+ in solution further revealed an additional coordination to Ca and Y in the 2-M n+ adducts with shortened Ni-M distances of 2.15 and 2.11 Å, respectively, implying direct bonding interactions between Ni and Lewis acids (LAs). Such a short interatomic distance between Ni(III) and M is unprecedented and was not observed before. EPR analysis of 2 and 2-M n+ species, moreover, displayed rhombic signals with g av > 2.12 for all complexes, supporting the +III oxidation state of Ni. The Ni III /Ni II redox potential of 2 and 2-M n+ species was determined, and a plot of E 1/ 2 of 2-M n+ versus pK a of [M(H 2 O) n ] m+ exhibited a linear relationship, implying that the Ni III /Ni II potential of 2 can be tuned with different redox-inactive metal ions. Reactivity studies of 2 and 2-M n+ with different 4-X-2,6-ditert-butylphenol (4-XDTBP) and other phenol derivatives were performed, and based on kinetic studies, we propose the involvement of a proton-coupled electron transfer (PCET) pathway. Analysis of the reaction products after the reaction of 2 with 4-OMe-DTBP showed the formation of a Ni(II) complex (1a) where one of the alkoxide arms of the ligand is protonated. A pK a value of 24.2 was estimated for 1a. The reaction of 2-M n+ species was examined with 4-OMe-DTBP, and it was observed that the k 2 values of 2-M n+ species increase by increasing the Lewis acidity of redox-inactive metal ions. However, the obtained k 2 values for 2-M n+ species are much lower compared to the k 2 value for 2. Such a variation of PCET reactivity between 2 and 2-M n+ species may be attributed to the interactions between Ni(III) and LAs. Our findings show the significance of the secondary coordination sphere effect on the PCET reactivity of Ni(III) complexes and furnish important insights into the reaction mechanism involving high-valent nickel species, which are frequently invoked as key intermediates in Ni-mediated enzymatic reactions, solar-fuel catalysis, and biomimetic/synthetic transformation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Combining Reactive Quantum-Mechanical Molecular-Dynamics Simulations with Mutagenesis, Crystallography, and Enzyme Kinetics to Reveal Plausible Steps of Isocyanide Hydratase Catalysis

A complete understanding of enzyme mechanisms requires atomistic details of chemical reactions. Quantum-based molecular dynamics simulations (QMD) are a potential source of this information, but trade-offs between accuracy and computational cost have limited their use. We previously developed extended Lagrangian Born–Oppenheimer molecular dynamics (XL-BOMD) methods that leverage a negligible compromise in accuracy to substantially decrease the cost of QMD simulations. Here, we develop a reactive QMD approach using the latest XL-BOMD formulation, which enables efficient simulations of highly reactive systems, and use it to investigate mechanisms of intermediate formation in isocyanide hydratase (ICH) catalysis. In QMD simulations, molecular analogs of ICH active site residues reacted with para-nitrophenyl isocyanide, forming a thioimidate. Analysis of simulated atomic configurational and charge dynamics revealed a pathway where protonation of the isocyanide carbon occurs prior to thioimidate formation and suggested a possible role of Asp17 as a proton donor in the early phase of ICH catalysis. To test whether the pathway seen using the reactive QMD approach might be relevant to ICH catalysis, we performed X-ray crystallography and pre-steady-state enzyme kinetics studies of wild-type and D17N mutant ICH. Both the structure and kinetics are sensitive to the D17N mutation in a manner that is consistent with the order of the reaction steps seen in the simulations. Mobile protons play essential roles in many enzymes, yet they are difficult to observe experimentally, making the ordering of proton-dependent steps ambiguous in many enzyme mechanisms. The ability to directly simulate model reactions for the design of experiments that provide information about enzyme mechanisms involving mobile protons demonstrates the significance of our reactive QMD approach and motivates further biological applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Recent Advances for Improving the Accuracy, Transferability, and Efficiency of Reactive Force Fields

Reactive force fields provide an affordable model for simulating chemical reactions at a fraction of the cost of quantum mechanical approaches. However, classically accounting for chemical reactivity often comes at the expense of accuracy and transferability, while computational cost is still large relative to nonreactive force fields. Here, we summarize recent efforts for improving the performance of reactive force fields in these three areas with a focus on the ReaxFF theoretical model. To improve accuracy, we describe recent reformulations of charge equilibration schemes to overcome unphysical long-range charge transfer, new ReaxFF models that account for explicit electrons, and corrections for energy conservation issues of the ReaxFF model. To enhance transferability we also highlight new advances to include explicit treatment of electrons in the ReaxFF and hybrid nonreactive/reactive simulations that make it possible to model charge transfer, redox chemistry, and large systems such as reverse micelles within the framework of a reactive force field. To address the computational cost, we review recent work in extended Lagrangian schemes and matrix preconditioners for accelerating the charge equilibration method component of ReaxFF and improvements in its software performance in LAMMPS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗