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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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All sourcesNASA NTRSDOE OSTI
NASA NTRS2005

X-Ray and Radio Studies of Black Hole X-Ray Transients During Outburst Decay

Black hole (BH) and black hole candidate (BHC) transients are X-ray binary systems that typically undergo bright outbursts that last a couple months with recurrence times of years to decades. For this ADP project, we are studying BH/BHC systems during the decaying phases of their outbursts using the Rossi X-ray Taming Explorer (RXTE), the Chandra X-ray Observatory, and multi-wavelength facilities. These systems usually undergo state transitions as they decay, and our observations are designed to catch the state transitions. The specific goals of this proposal include: 1. To determine the evolution of the characteristic frequencies present in the power spectrum (such as quasi-periodic oscillations, QPOs) during state transitions in order to place constraints on the accretion geometry; 2. To contemporaneously measure X-ray spectral and timing properties along with flux measurements in the radio band to determine the relationship between the accretion disk and radio jets; 3. To extend our studies of X-ray properties of BHCs to very low accretion rates using RXTE and Chandra. The work performed under this proposal has been highly successful, allowing the PI to lead, direct, or assist in the preparation of 7 related publications in refereed journals and 6 other conference presentations or reports. These items are listed below, and the abstracts for the refereed publications have also been included. Especially notable results include our detailed measurements of the characteristic frequencies and spectral parameters of BH/BHCs after the transition to the hard state (see All A3, and A5) and at low flux levels (see A4). Our measurements provide one of the strongest lines of evidence to date that the inner edge of the optically thick accretion disk gradually recedes from the black hole at low flux levels. In addition, we have succeeded in obtaining excellent multi-wavelength coverage of a BH system as its compact jet turned on (see Al). Our results show, somewhat unexpectedly, that the radio jet does not turn on until the hard X-ray emission is well past its peak hard state level, strongly constraining theoretical models for hard X-ray production and the spectrum emitted by the jet. Finally, the X-ray/radio results in A2 led us to propose a general picture about the relationship between jet production and X-ray spectral states .

Tomsick, John A.↗
DOE OSTI2022

A Combined DFT, Energy Decomposition, and Data Analysis Approach to Investigate the Relationship Between Noncovalent Interactions and Selectivity in a Flexible DABCOnium/Chiral Anion Catalyst System

Developing strategies to study reactivity and selectivity in flexible catalyst systems has become an important topic of research. Herein, we report a combined experimental and computational study aimed at understanding the mechanistic role of an achiral DABCOnium cofactor in a regio- and enantiodivergent bromocyclization reaction. In this study, it was found that electron-deficient aryl substituents enable rigidified transition states via an anion–π interaction with the catalyst, which drives the selectivity of the reaction. In contrast, electron-rich aryl groups on the DABCOnium result in significantly more flexible transition states, where interactions between the catalyst and substrate are more important. An analysis of not only the lowest-energy transition state structures but also an ensemble of low-energy transition state conformers via energy decomposition analysis and machine learning was crucial to revealing the dominant noncovalent interactions responsible for observed changes in selectivity in this flexible system.

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

The reaction NH 2 + CH 2 O: Kinetic measurements and computational studies

The reaction of amidogen with formaldehyde is relevant to astrochemistry and couples nitrogen and carbon chemistry in flames. The first measurements of the temperature dependence of the rate constant k were made, over 409–643 K, and are summarized as k = 7.1 × 10 −12 exp(−18.2 kJ mol −1 /RT) cm 3 molecule −1 s −1 with a confidence interval of ±20%. These results address a controversy over the presence of a significant barrier in the addition/elimination pathway leading to the production of formamide between theoretical models that include the zero-point energy of all modes at the transition state and a model that excludes transitional modes. The latter would lead to a negligible barrier, which is inconsistent with the experiments. Contrary to earlier claims, CCSDT(Q)-corrected energies combined with transition state theory yield quantitative accord with the measurements.

Astrochemistry↗
DOE OSTI2024

High-Pressure Rate Rules for Ether Alkylperoxy Radical Isomerization

The first isomerization reaction of an alkylperoxy (RO 2 ) radical holds significant importance in low-temperature oxidation, as it governs the branching ratios of the hydroperoxyalkyl (QOOH) radicals, which influence the competition between the chain-propagation and chain-branching reactions. In this study, we systematically calculated high-pressure rate rules for the RO 2 isomerization reaction of monoethers, exploring 5-, 6-, 7-, and 8-membered ring transition states. Primary, secondary, and tertiary carbon sites, where both the abstracting peroxy group and the abstracted hydrogen are located, were considered, with particular emphasis on distinguishing between secondary carbons adjacent (alpha) and nonadjacent to the ether functional group. Using the G4//B3LYP/6-311++G(2df,2pd) level of theory and the transition state theory, we estimated the rate constants and the Arrhenius coefficient for over 120 possible isomerization reactions. We examined the effect of ring size and ring atoms, revealing that 6- and 7-membered ring isomerizations were generally the fastest. The impact of the ether functional group on transition states was investigated by comparing reactions with identical ring size, peroxy, and radical positions, but with the ether functional group positioned either outside (i.e., out) or inside (i.e., in) the transition state ring, leading to differences in the rate constants. When comparing to analogous alkane rate constants, differences of up to an order of magnitude were observed, underscoring the need for caution when assigning rate rules by analogy. We applied our rate constants in the di-iso-butyl ether kinetic model and evaluated their influence on low-temperature chemistry finding that they altered the branching ratios by up to a factor of 9, highlighting the significance of site-specific rate constants for more accurate low-temperature modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Importance of finite-size corrections for accurate ab initio modeling of carrier capture at semiconductor defects: A case study of substitutional C N in GaN

In ab initio studies of carrier-capture processes in defective semiconductor materials, the single-effective-mode formalism and the static-coupling approximation have become the predominant theoretical approaches for determining carrier-capture coefficients. The single-mode formalism relies on accurate nonequilibrium defect energies obtained from density-functional theory (DFT), where required inputs are a series of configurationally displaced, defect-containing supercells obtained using an interpolative ansatz, and where the DFT outputs are corresponding total energies that have traditionally been postprocessed using a long-established ground-state formulation of finite-size corrections and defect-formation energies. This formulation remains commonly used even though the defects that form a configuration-coordinate (CC) diagram typically exist as structures that are displaced from the ground state. To remedy this inconsistency, Kumagai has recently proposed novel methods for implementing finite-size corrections specifically intended for DFT calculations of the defect energies used to construct CC diagrams and implement the single-mode formalism [Y. Kumagai, Phys. Rev. B 107, L220101 (2023)]. Kumagai's approach builds on the latest finite-size-correction methods introduced to describe vertical charge-state transitions for charge-localizing point defects in semiconductors and insulators [T. Gake et al., Phys. Rev. B 101, 020102 (2020); S. Falletta et al., Phys. Rev. B 102, 041115 (2020)]. The newly identified finite-size artifact treated in these studies is the polarization charge induced on a configurationally frozen defect and its subsequent interaction with a vertical transition in charge state. In this work, we evaluate Kumagai's proposed methodology by applying it in a high-precision DFT study of carrier capture by substitutional C N in GaN, a well-characterized and technologically relevant defect and material. We have rigorously calculated C N defect energies across various supercell sizes for each defect configuration and charge state on the hole-capture CC diagram of C N (𝑞=−1), enabling a direct comparison of the slopes of the defect energies versus inverse cell size with those predicted by Kumagai. The most consequential prediction of Kumagai's method is that these slopes distinctly vary as the square of the linear-interpolation parameter used to construct the nonequilibrium defect configurations. Our results quantitatively support this prediction. Moreover, with these new finite-size corrections and multiple-cell-size DFT calculations in place, we find that the classical energy barrier for hole capture by C N (𝑞=−1) in GaN decreases to 0.092–0.127 eV. This finding confirms the recent ≈ 0.1 eV prediction of Reshchikov based on the weak temperature dependence for hole capture observed in photoluminescence experiments [M. A. Reshchikov, J. Appl. Phys. 129, 121101 (2021)]. These results stand in stark contrast to previously calculated barriers of 0.486 and 0.73 eV, which also used the single-mode formalism but were obtained by instead using ground-state-based finite-size corrections. Our reduced classical barrier for capture increases the temperature-dependent hole-capture coefficient of a C N (𝑞=−1) defect by more than two to four orders of magnitude for temperatures of 100–600 K, compared to the previous 0.486 eV results. While other defects may not be as dramatically affected as here, we suggest that incorporating proper finite-size corrections for the vertical-transition-like states embedded within CC diagrams is an essential, yet previously unrecognized, component of accurate modeling of carrier-capture when using the single-effective-mode formalism.

dielectric properties↗
NASA NTRS1981

An algorithm for minimum-cost set-point ordering in a cryogenic wind tunnel

An algorithm for minimum cost ordering of set points in a cryogenic wind tunnel is developed. The procedure generates a matrix of dynamic state transition costs, which is evaluated by means of a single-volume lumped model of the cryogenic wind tunnel and the use of some idealized minimum-costs, which is evaluated by means of a single-volume lumped model of the cryogenic wind tunnel and the use of some idealized minimum-cost state-transition control strategies. A branch and bound algorithm is employed to determine the least costly sequence of state transitions from the transition-cost matrix. Some numerical results based on data for the National Transonic Facility are presented which show a strong preference for state transitions that consume to coolant. Results also show that the choice of the terminal set point in an open odering can produce a wide variation in total cost.

Tripp, J. S.↗
NASA NTRS2000

Closed-form integrator for the quaternion (euler angle) kinematics equations

The invention is embodied in a method of integrating kinematics equations for updating a set of vehicle attitude angles of a vehicle using 3-dimensional angular velocities of the vehicle, which includes computing an integrating factor matrix from quantities corresponding to the 3-dimensional angular velocities, computing a total integrated angular rate from the quantities corresponding to a 3-dimensional angular velocities, computing a state transition matrix as a sum of (a) a first complementary function of the total integrated angular rate and (b) the integrating factor matrix multiplied by a second complementary function of the total integrated angular rate, and updating the set of vehicle attitude angles using the state transition matrix. Preferably, the method further includes computing a quanternion vector from the quantities corresponding to the 3-dimensional angular velocities, in which case the updating of the set of vehicle attitude angles using the state transition matrix is carried out by (a) updating the quanternion vector by multiplying the quanternion vector by the state transition matrix to produce an updated quanternion vector and (b) computing an updated set of vehicle attitude angles from the updated quanternion vector. The first and second trigonometric functions are complementary, such as a sine and a cosine. The quantities corresponding to the 3-dimensional angular velocities include respective averages of the 3-dimensional angular velocities over plural time frames. The updating of the quanternion vector preserves the norm of the vector, whereby the updated set of vehicle attitude angles are virtually error-free.

Whitmore, Stephen A.↗
NASA NTRS2009

Model Checking - My 27-Year Quest to Overcome the State Explosion Problem

Model Checking is an automatic verification technique for state-transition systems that are finite=state or that have finite-state abstractions. In the early 1980 s in a series of joint papers with my graduate students E.A. Emerson and A.P. Sistla, we proposed that Model Checking could be used for verifying concurrent systems and gave algorithms for this purpose. At roughly the same time, Joseph Sifakis and his student J.P. Queille at the University of Grenoble independently developed a similar technique. Model Checking has been used successfully to reason about computer hardware and communication protocols and is beginning to be used for verifying computer software. Specifications are written in temporal logic, which is particularly valuable for expressing concurrency properties. An intelligent, exhaustive search is used to determine if the specification is true or not. If the specification is not true, the Model Checker will produce a counterexample execution trace that shows why the specification does not hold. This feature is extremely useful for finding obscure errors in complex systems. The main disadvantage of Model Checking is the state-explosion problem, which can occur if the system under verification has many processes or complex data structures. Although the state-explosion problem is inevitable in worst case, over the past 27 years considerable progress has been made on the problem for certain classes of state-transition systems that occur often in practice. In this talk, I will describe what Model Checking is, how it works, and the main techniques that have been developed for combating the state explosion problem.

Clarke, Ed↗
DOE OSTI2025

Criegee Intermediates Compete Well with OH as a Cleaning Agent for Atmospheric Amides

Elucidating the chemical kinetics of stabilized Criegee intermediates (sCIs) in the atmosphere is critically important for climate modeling. Here, we report a class of very rapid bimolecular reactions of two sCIs, namely, CH 2 OO and syn-CH 3 CHOO, with amides. We used electronic structure calculations and kinetics calculations to elucidate a universal mechanism by which the oxygen atom of the carbonyl group in an amide is added to the carbon atom of the COO group in the sCI with simultaneous transfer of the amide hydrogen to the terminal oxygen atom of the carbonyl oxide of the sCI. The barriers for the mechanism are submerged below reactants by ∼9 kcal/mol, which means that the tight transition state is not the rate-determining step, and the rate constants are determined by loose free energy bottlenecks between the reactants and the precursor complexes. We calculate the rate constants due to these loose and barrierless transition states by variable-reaction-coordinate variational transition-state theory. We find that bimolecular reactions of sCIs with amides are very rapid, with rate constants 1 to 5 × 10 –10 cm 3 molecule –1 s –1 , which is a factor of 2 faster than the rate constants of carboxylic acids with sCIs and 10 2 faster than the rate constants of OH reactions with amides. This has the consequence that, under a wide range of conditions, sCIs are the major sink for atmospheric amides, in contrast to the usual assumption that OH radicals are the dominant sinks.

Amides↗
DOE OSTI2020

On the origin of ground-state vacuum-field catalysis: Equilibrium consideration

Recent experiments suggest that vibrational strong coupling (VSC) may significantly modify ground-state chemical reactions and their rates even without external pumping. The intrinsic mechanism of this “vacuum-field catalysis” remains largely unclear. Generally, modifications of thermal reactions in the ground electronic states can be caused by equilibrium or non-equilibrium effects. The former are associated with modifications of the reactant equilibrium distribution as expressed by the transition state theory of chemical reaction rates, while the latter stem from the dynamics of reaching and leaving transition state configurations. In this work, we examine how VSC can affect chemical reactions rates in a cavity environment according to transition state theory. Our approach is to examine the effect of coupling to cavity mode(s) on the potential of mean force (PMF) associated with the reaction coordinate. Within the context of classical nuclei and classical photons and also assuming no charge overlap between molecules, we find that while the PMF can be affected by the cavity environment, this effect is negligible for the usual micron-length cavities used to examine VSC situations.

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

Infrared Fingerprint and Unimolecular Decay Dynamics of the Hydroperoxyalkyl Intermediate (•QOOH) in Cyclopentane Oxidation

A transient carbon-centered hydroperoxyalkyl intermediate (•QOOH) in the oxidation of cyclopentane is identified by IR action spectroscopy with time-resolved unimolecular decay to hydroxyl (OH) radical products that are detected by UV laser-induced fluorescence. Two nearly degenerate •QOOH isomers, β- and γ-QOOH, are generated by H atom abstraction of the cyclopentyl hydroperoxide precursor. Fundamental and first overtone OH stretch transitions and combination bands of •QOOH are observed and compared with anharmonic frequencies computed by second-order vibrational perturbation theory. An OH stretch transition is also observed for a conformer arising from torsion about a low-energy CCOO barrier. Definitive identification of the β-QOOH isomer relies on its significantly lower transition state (TS) barrier to OH products, which results in rapid unimolecular decay and near unity branching to OH products. A benchmarking approach is utilized to compute high-accuracy stationary point energies, most importantly TS barriers, for cyclopentane oxidation (C 5 H 9 O 2 ), building on higher level reference calculations for ethane oxidation (C 2 H 5 O 2 ). The experimental OH product appearance rates are compared with computed statistical microcanonical rates using RRKM theory, including heavy-atom tunneling, thereby validating the computed TS barrier. The results are extended to thermal unimolecular decay rate constants at temperatures and pressures relevant to cyclopentane combustion via master-equation modeling. Furthermore, the various torsional and ring puckering states of the wells and transition states are explicitly considered in these calculations.

Chemical calculations↗
NASA NTRS2012

Three years of Transients with Fermi GBM

The Gamma-ray Burst Monitor (GBM) is an all-sky monitoring instrument, sensitive between 8 keV and 40 MeV, with a primary objective of supporting the Large Area Telescope (LAT) in observations of Gamma-Ray Bursts (GRBs). Both instruments are part of the Fermi Gamma-ray Space Telescope. Together, the GBM and LAT instruments have provided ground-breaking measurements of GRBs that have, after 10 years of focus on GRB afterglows, inspired renewed interest in the prompt emission phase of GRBs and the physical mechanisms that fuel them. In addition to GRB science, GBM has made significant contributions to the astrophysics of galactic transient sources including long-term variations in the Crab nebula, spin state transitions in accretion powered pulsars, state transitions in black hole X-ray binaries, and unprecedented time-resolved spectral studies of soft gamma-ray repeater bursts. Closer to home, GBM also contributes to solar flare and terrestrial gamma flash science.

Wilson-Hodge, Colleen A.↗
DOE OSTI2025

How Solvent Mediates the Catalytic Fate of 2-Methoxyphenol in Hydrodeoxygenation Catalysis?

Kinetic and isotopic assessments combined with theoretical calculations shed light on the mechanistic differences in terms of the number of hydrogen addition steps and the electronic charges of reactive hydrogen in the catalytic sequence leading to the Ar−OCH 3 scission of 2-methoxyphenol occurring at various interfaces of vapor−Ru, cyclohexane−Ru, and water−Ru. At vapor−Ru and cyclohexane−Ru interfaces, the initial hydrogen adatom (H*) additions on the phenyl ring disrupt its aromaticity, as a step required to occur before kinetically relevant Ar−OCH 3 scission on an ensemble of Ru sites. The number of H* addition events prerequisite to the formation of the kinetically relevant Ar−OCH 3 scission transition state, however, is larger at the cyclohexane−Ru interface than those at the vapor−Ru and water−Ru interfaces. The preferential solvation of 2-methoxyphenol derived reaction precursors and H* weakens their adsorption on Ru sites, which leads to a decrease in the activation barrier for the third H* addition step and in turn a larger number of H* additions. At the water−Ru interface, water as a polar protic solvent promotes the Ar−OCH 3 scission by enabling a mechanistically distinct catalytic route an adjacent water molecule from the solvent layer assists with the intramolecular proton shuttling from the hydroxyl group (−OH) to the vicinal methoxy group (−OCH 3 ) of 2-methoxyphenol, evolving a highly charged transition state that is further stabilized by the water solvent layer, thereby leading to Ar−OCH 3 scission rate constants that are much higher than those at the vapor−Ru interface and, when comparing at the same H 2 chemical potential, higher Ar−OCH 3 scission turnovers. Furthermore, these distinct mechanistic details of the Ar−OCH 3 scission at various reaction interfaces, inferred from experiment and theory, illustrate how a solvent either solvates reaction intermediates and transition states or directly participates in the formation of kinetically relevant transition states, leading to changes in the free energy landscape, thus rewriting the catalytic fates in hydrodeoxygenation reactions.

09 BIOMASS FUELS↗
DOE OSTI2023

Promotion of adsorptive and catalytic properties of zeolitic Brønsted acid sites by proximal extra-framework Si(OH) x groups

Steric confinement in zeolites influences the catalytic conversion of alkanes. For zeolitic Brønsted acid sites, proximate extra-framework species introduce additional confinement to the pore constraints, enhancing the catalytic activity of alkane cracking. Although extra-framework alumina has been the most studied, here we report the element-specific impact of silica species. Further, by grafting extra-framework silica species close to Brønsted acid sites in H-ZSM-5 zeolite, the binding of bases like pyridine and amines is strengthened via van der Waals interactions with their aryl or alkyl chains. Brønsted acid sites close to extra-framework silica achieve a higher reaction rate of protolytic cracking of n-pentane via enthalpic (unlike entropic, as with extra-framework alumina) stabilization of the transition state by 24–51 kJ mol −1 . The lower activation energy points to an earlier transition state than in the presence of extra-framework alumina, with a better stabilization of the carbonium ions in the transition state compared to the parent zeolite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Algorithmic improvements for simulator motion drive

Contemporary simulator motion drive algorithms typically are designed in an analog (continuous) environment, but are implemented in a digital (discrete) environment. The intended continuous system, specified as frequency domain (Laplace transform) transfer functions, may not be represented properly by the algorithms used for digital implementation. The motion drive software in use with the Vertical Motion Simulator at Ames Research Center was investigated recently; the original algorithms (Euler) were changed to a state transition method. Comparison of the frequency responses of the original and new implementations showed that the state transition method more closely approximates the desired analog responses. In addition, test pilots who evaluated both implementations preferred the motions generated with the state transition method over those generated with the Euler integration method.

Laforce, Soren↗
DOE OSTI2021

Hydrogenation and C-S bond activation pathways in thiophene and tetrahydrothiophene reactions on sulfur-passivated surfaces of Ru, Pt, and Re nanoparticles

Thiophene-H2 reactions proceed via sulfur removal and hydrogenation routes on dispersed metal nanoparticles that become decorated by refractory S-adlayers during catalysis. The identity and kinetic relevance of the required elementary steps are described here based on rates measured at S-chemical potentials set by H2S/H2 ratios similar to those prevalent during practical catalysis on Re, ReSx, Ru, and Pt catalysts. Free energies for S adatom formation (from H2S decomposition and H2 evolution) are strongly exothermic (< -50 kJ mol-1 on Pt(111) and < -150 kJ mol-1 on Re and Ru(0001)), but strong repulsions between S adatoms cause adsorption free energies to increase significantly with coverage on all three surfaces, preventing complete monolayer formation. These adlayers, composed of unreactive S-atoms (S') that cover 1/3–2/3 ML leave residual interstitial spaces (*) that bind S-atoms (S*), intermediates, and transition states reversibly, as required for catalytic turnovers. The number and binding properties of these interstices depend on the identity and chemical state of the nanoparticle bulk phase, which influences S'-binding and coverages and cause large differences in direct desulfurization and hydrogenation turnover rates (per exposed metal atom) on dispersed Re, ReSx, Ru, and Pt. The identity and kinetic relevance of elementary steps for desulfurization (to C4¬ hydrocarbons) and hydrogenation (to tetrahydrothiophene; THT) are similar among these catalysts; they involve the kinetically-relevant formation of a thiophene-derived intermediate (monohydrothiophene on Re and ReSx; dihydrothiophene on Ru and Pt) that either cleaves its C-S bond or “over-hydrogenates” to THT in one surface sojourn. THT then undergoes C-S bond cleavage in secondary reactions that correct such over-hydrogenation to form the more unsaturated species that cleave C-S bonds. THT/C4 product ratios are insensitive to H2S/H2 ratios and thiophene pressure, even though active interstitial spaces are covered by kinetically-detectable coverages of S* and thiophene; therefore, primary and secondary reactions must involve the same active surfaces. The observed increase in THT/C4 ratios with H2 pressure shows that THT formation transition states involve a larger number of H-atoms than for C-S cleavage. The requirement for bound species with intermediate unsaturation (between THT and thiophene) for C-S bond cleavage is reminiscent of the H-shuttling required in C-C and C-O hydrogenolysis, reactions that involve the partial dehydrogenation of alkanes and alkanols, respectively, to weaken such bonds and to increase the formation entropy of the relevant transition states via the evolution of H2(g). These mechanistic details challenge prevalent paradigms about different site requirements for hydrogenation and desulfurization pathways and about how metal-sulfur bond energies act as descriptors of reactivity; in fact, such binding energies merely act to define the refractory S-adlayers that enable the formation of weakly-binding interstices that reversibly bind intermediates and transition states, thus allowing catalytic turnovers.

Yik, Edwin↗
DOE OSTI2023

Operation Optimization using Reinforcement Learning with Integrated Artificial Reasoning Framework

In large and complex systems, operational decision-making requires a systematic analysis with a vast amount of data from both process parameters and component status monitoring. In this paper, we present an integrated artificial reasoning approach for system state transition models that can help operational decision-making with explainable and traceable reasoning. The integrated artificial reasoning framework is a physics-based approach of defining the system structure in a Bayesian network, so we leveraged it in a Markov decision process (MDP) for finding optimal operational solutions. In our proposed framework, the MDP is implemented on a dynamic Bayesian network (DBN), which represents causalities in a system. The multilevel flow modeling was utilized in order to extract these causalities in a more efficient and objective manner. Since multilevel flow modeling is based on the fundamental energy and mass conservation laws, the target system is decomposed into several mass, energy, and information structures, which serve as the basis for a DBN. The MDP consists of the processes of finding a solution for the Bellman equation, which can be derived from the conditional probability equations of the constructed DBN. System operators can capture stochastic system dynamics as multiple subsystem state transitions based on their physical relations and uncertainties coming from the component degradation process or random failures. We analyzed a simplified example system to illustrate finding an optimal operational policy with this approach.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2022

Steric and Lewis Basicity Influence of the Second Coordination Sphere on Electrocatalytic CO 2 Reduction by Manganese Bipyridyl Complexes

This study aims to provide a greater insight into the balance between steric (bpy vs (Ph) 2 bpy vs mes 2 bpy ligands) and Lewis basic ((Ph) 2 bpy vs (MeOPh) 2 bpy vs (MeSPh) 2 bpy ligands) influence on the efficiencies of the protonation-first vs reduction-first CO 2 reduction mechanisms with [Mn I (R 2 bpy)(CO) 3 (CH 3 CN)] + precatalysts, and on their respective transition-state geometries/energies for rate-determining C–OH bond cleavage toward CO evolution. The presence of only modest steric bulk at the 6,6'-diphenyl-2,2'-bipyridyl ((Ph) 2 bpy) ligand has here allowed unique insight into the mechanism of catalyst activation and CO 2 binding by navigating a perfect medium between the nonsterically encumbered bpy-based and the highly sterically encumbered mes2bpy-based precatalysts. Cyclic voltammetry conducted in CO 2 -saturated electrolyte for the (Ph) 2 bpy-based precatalyst [2-CH 3 CN] + confirms that CO 2 binding occurs at the two-electron-reduced activated catalyst [2] – in the absence of an excess proton source, in contrast to prior assumptions that all manganese catalysts require a strong acid for CO 2 binding. This observation is supported by computed free energies of the parent–child reaction for [Mn–Mn] o dimer formation, where increased steric hindrance relative to the bpy-based precatalyst correlates with favorable CO 2 binding. A critical balance must be adhered to, however, as the absence of steric bulk in the bpy-based precatalyst [1-CH 3 CN] + maintains a lower overpotential than [2-CH 3 CN] + at the protonation-first pathway with comparable kinetic performance, whereas an ~2-fold greater TOF max is observed at its reduction-first pathway with an almost identical overpotential as [2-CH 3 CN] + . Notably, excessive steric bulk in the mes2bpy-based precatalyst [3-CH 3 CN] + results in increased activation free energies of the C–OH bond cleavage transition states for both the protonation-first and the reduction-first pathways relative to both [1-CH 3 CN] + and [2-CH 3 CN] + . In fact, [3-CH 3 CN] + requires a 1 V window beyond its onset potential to reach its peak catalytic current, which is in contrast to the narrower (<0.30 V) potential response window of the remaining catalysts here studied. Furthermore, voltammetry recorded under 1 atm of CO 2 with 2.8 M (5%) H 2 O establishes [2-CH 3 CN] + to have the lowest overpotential (η = 0.75 V) in the series here studied, attributed to its ability to lie “on the fence” when providing sufficient steric bulk to hinder (but not prevent) [Mn–Mn] o dimerization, while simultaneously having a limited steric impact on the free energy of activation for the rate-determining C–OH bond cleavage transition state. While the methoxyphenyl bpy-based precatalyst [4-CH 3 CN] + possesses an increased steric presence relative to [2-CH 3 CN] + , this is offset by its capacity to stabilize the C–OH bond cleavage transition states of both the protonation-first and the reduction-first pathways by facilitating second coordination sphere H-bonding stabilization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗