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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Nonadiabatic couplings from a variational excited state method based on constrained DFT

Excited Costrained Density Functional Theory (XCDFT) is a variational excited state method that extends ground state DFT to the computation of low-lying excited states. It borrows much of the machinery of Constrained DFT (CDFT) with a crucial difference: the constraint imposes a population of one electron in the Hilbert space spanned by the virtuals of a reference ground state. Here, we present theory and implementation for evaluating nonadiabatic coupling vectors (NACVs) between the first excited state computed with XCDFT and the ground state. Our NACVs are computed analytically using density functional perturbation theory with a formalism that is general enough that could be applied to CDFT diabatic states. We showcase the new method with pilot NACV calculations for the conical intersection in H 3 , the avoided crossing in selenoacrolein, and the NACV magnitudes in azobenzene. Despite complications from the nonorthogonality of the wavefunctions, XCDFT’s energy surfaces and NACVs reproduce benchmark values and respect known sum rules within a reasonable degree. This shows that XCDFT is a viable method for nonadiabatic dynamics simulations.

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

Iron Impurity Impairs the CO 2 Capture Performance of MgO: Insights from Microscopy and Machine Learning Molecular Dynamics

Magnesium oxide (MgO) is a promising sorbent for direct air capture (DAC) of carbon dioxide. Iron (Fe) is a common impurity in naturally occurring MgO and minerals used to produce MgO, yet a molecular-scale understanding of Fe-doping effects on carbonation is lacking. Here, in this study, we observed reduced carbonation performance in Fe-doped MgO experimentally. The energetics of adsorbing a (bi)carbonate ion on pristine and Fe-doped MgO(001) surfaces were further investigated using ab initio and machine learning potential molecular dynamics coupled with metadynamics simulations. Both pristine and Fe-doped surfaces exhibited a basic (OH – ) hydration layer, where the (bi)carbonate ion adsorption is thermodynamically favorable. However, the dissolution of surface Fe had smaller energy barriers and was more favorable than Mg. Leached Fe likely neutralized the near-surface basicity, yielding reduced reactivity on Fe-doped MgO. Our observations offer critical insights for material selection and emphasize the importance of evaluating the geologic origin of earth materials used for DAC.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Initial Assessment of TeF 6 Adsorption

Research and development that supports the management of off-gases from nuclear fuel reprocessing has historically been focused on the off-gas streams that arise from aqueous reprocessing technology. However, as Gen-IV reactor development pathways move toward deployment, alternative spent nuclear fuel (SNF) processing and disposition pathways have been considered more actively. This work is focused upon aspects of fluoride volatility (FV) processing. The versatility of this method for deployment against multiple types of spent fuel encourages the continued advancement of both the primary separations processes and the secondary processes, including waste treatment, material control and accountability, and engineering designs. Recent work noted that TeF 6 , the most highly volatile fluorinated compound produced during FV processing, did not have a clear abatement technology recommended in the literature. Thus, this work performed scoping tests on activated alumina and copper shot to assess whether they could be used to remove TeF 6 from gas streams that bear F 2 . Previous work on this topic was not well described in the literature and was not performed with excess F 2 in the stream as would be typical of spent fuel processing via FV. To support an understanding of the concentration of TeF 6 contacting the adsorbent beds, a series of preliminary testing identified the TeF 6 production rate and the equilibrium concentration of TeF 6 in the gas stream contacting the adsorbent. Excess F 2 was determined to not affect the ability of activated alumina to remove TeF 6 from the gas stream quickly and completely. A determination of whether excess F 2 affected the distribution depth of Te in the sorbent bed is still pending analysis of the used sorbent. Literature suggests that when activated alumina is near saturation, TeF 6 could migrate from the sorbent bed. Future testing should investigate this possibility. Copper metal did not adsorb TeF 6 in the presence of F 2 across the sorbent temperature range of 50 to 335°C. F 2 was fully removed by the copper bed. Although preliminary thermodynamics would indicate adsorption to be energetically favorable, other factors that impact adsorption (e.g., slow kinetics, excess fluorine on the copper surface, an unfavorable transition state) are likely preventing the adsorption of TeF 6 at an easily measurable rate. The work also investigated TeF 6 production from multiple forms of Te in the temperature range of 100 to 250°C. No previous study had assessed the initial reaction rates for this process. A carefully designed study allowed determination of the activation energy for the production of TeF 6 from Te metal. The substantial amount of data collected during this study merits analysis beyond what is described here. A more in-depth kinetic analysis will be pursued. Additional analytical results will provide the ability to benchmark adsorption coefficients for TeF 6 , understand the distribution of TeF 6 within the alumina bed, and better understand the effect of F 2 partial pressure on Te fluorination. The data from this report, as supplemented by these additional analyses, will be submitted to a peer-reviewed journal.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1982

Research on planetary samples

Sputtering yields of solid SO2 by high energy ions were measured in order to study the mechanism for sputtering dielectrics with ions in the electronic stopping power region. The incident ions were helium and fluorine with energies ranging from 1.5 MeV to 25 MeV. Yields as high as 7000 SO2 molecules/incident F ion were measured; the 1.5 MeV He4 beam had a sputtering yield of 50. The data are compared to yield measurements made on UF4 and H2O targets. There is a striking similarity in the yield as a function of the Energy for all three targets. The data compare favorably with theoretical curves based on a model for the sputtering which considers the electronic excitations induced the target by the incident beam. Measurements and calculations of the sort are also useful in understanding processes which occur on the surface of Jupiter's satellite Io, which is covered with SO2 frost and bombarded by energetic ions trapped in the Jovian magnetosphere.

Tombrello, T. A.↗
NASA NTRS1983

Sputtering of SO2 by high energy ions

Sputtering yields of solid SO2 by high energy ions were measured in order to study the mechanism for sputtering dielectrics with ions in the electronic stopping power region. The incident ions were helium and fluorine with energies ranging from 1.5 MeV to 25 MeV. Yields as high as 7000 SO2 molecules/incident F ion were measured; the 1.5 MeV He-4 beam had a sputtering yield of 50. The data are compared to yield measurements made on UF4 and H2O targets. There is a striking similarity in the yield as a function of the incident F energy for all three targets. The data compare favorably with theoretical yield curves based on a new model for the sputtering which considers the electronic excitations induced in the target by the incident beam. Measurements and calculations of this sort are also useful in understanding processes which occur on the surface of Jupiter's satellite Io, which is covered with SO2 frost and bombarded by energetic ions trapped in the Jovian magnetosphere.

Lepoire, D. J.↗
NASA NTRS1997

Atmospheric Angular Momentum Fluctuations During 1979-1988 Simulated by Global Circulation Models

Changes in major global dynamical phenomena in the Earth's atmosphere are manifested in the time series of atmospheric angular momentum (AAM), as determined directly from meteorological observations and indirectly from geodetic observations of small fluctuations in the rotation of the solid Earth which are proportional to length of day. AAM fluctuations are intimately linked with energetic processes throughout the whole atmosphere and also with the stresses at the Earth's surface produced largely by turbulent momentum transport in the oceanic and continental boundary layers and by the action of normal pressure forces on orographic features. A stringent test of any numerical global circulation model (GCM) is therefore provided by a quantitative assessment of its ability to represent AAM fluctuations on all relevant timescales, ranging from months to several years. From monthly data provided by the Atmospheric Model Intercomparison Project (AMIP) of the World Climate Research Programme, we have investigated seasonal and interannual fluctuations and the decadal mean in the axial component of AAM in 23 AMIP GCMs over the period 1979-1988. The decadal means are generally well simulated, with the model median value (1.58 x 10(exp 26) kg sq m/s) being only 3.5% larger than the observed mean and with 10 of the models being within 5% of the observed. The seasonal cycle is well reproduced, with the median amplitude of the models seasonal standard deviations being only 2.4% larger than observed. Half the seasonal amplitudes lie within 15% of the observed, and the median correlation found between the observed and model seasonal cycles is 0.95. The dominant seasonal error is an underestimation of AAM during northern hemisphere winter associated with errors in the position of subtropical jets. Less robust are the modeled interannual variations, although the median correlation of 0.61 between model simulations and observed AAM is statistically significant. The two El Nino-Southem Oscillation events that occurred during the AMIP decade 1979-1988 have the expected positive AAM anomalies, although the AAM signature of the 1982-1983 event tends to be underestimated and that of the 1986-1987 event overestimated.

Hide, R.↗
NASA NTRS1997

Atmospheric Angular Momentum Fluctuations During 1979-1988 Simulated by Global Circulation Models

Changes in major global dynamical phenomena in the Earth's atmosphere are manifested in the time series of atmospheric angular momentum (AAM), as determined directly from meteorological observations and indirectly from geodetic observations of small fluctuations in the rotation of the solid Earth which are proportional to length of day. AAM fluctuations are intimately linked with energetic processes throughout the whole atmosphere and also with the stresses at the Earth's surface produced largely by turbulent momentum transport in the oceanic and continental boundary layers and by the action of normal pressure forces on orographic features. A stringent test of any numerical global circulation model (GCM) is therefore provided by a quantitative assessment of its ability to represent AAM fluctuations on all relevant timescales, ranging from months to several years. From monthly data provided by the Atmospheric Model Intercomparison Project (AMIP) of the World Climate Research Programme, we have investigated seasonal and interannual fluctuations and the decadal mean in the axial component of AAM in 23 AMIP GCMs over the period 1979-1 988. The decadal means are generally well simulated, with the model median value (1.58 x 10(exp 26) kg sq m/s) being only 3.5% larger than the observed mean and with 10 of the models being within 5% of the observed. The seasonal cycle is well reproduced, with the median amplitude of the models' seasonal standard deviations being only 2.4% larger than observed. Half the seasonal amplitudes lie within 15% of the observed, and the median correlation found between the observed and model seasonal cycles is 0.95. The dominant seasonal error is an under- estimation of AAM during northern hemisphere winter associated with errors in the position of subtropical jets. Less robust are the modeled interannual variations, although the median correlation of 0.61 between model simulations and observed AAM is statistically significant. The two El Nino-Southern Oscillation events that occurred during the AMIP decade 1979-1988 have the expected positive AAM anomalies, although the AAM signature of the 1982-1983 event tends to be underestimated and that of the 1986-1987 event overestimated.

Hide, R.↗
NASA NTRS2000

DSMC Simulation of Separated Flows About Flared Bodies at Hypersonic Conditions

This paper describes the results of a numerical study of interacting hypersonic flows at conditions that can be produced in ground-based test facilities. The computations are made with the direct simulation Monte Carlo (DSMC) method of Bird. The focus is on Mach 10 flows about flared axisymmetric configurations, both hollow cylinder flares and double cones. The flow conditions are those for which experiments have been or will be performed in the ONERA R5Ch low-density wind tunnel and the Calspan-University of Buffalo Research Center (CUBRC) Large Energy National Shock (LENS) tunnel. The range of flow conditions, model configurations, and model sizes provides a significant range of shock/shock and shock/boundary layer interactions at low Reynolds number conditions. Results presented will highlight the sensitivity of the calculations to grid resolution, contrast the differences in flow structure for hypersonic cold flows and those of more energetic but still low enthalpy flows, and compare the present results with experimental measurements for surface heating, pressure, and extent of separation.

Moss, James N.↗
NASA NTRS2001

Low Temperature Reflectance Spectra of Titan Tholins

Compositional interpretation of remotely obtained reflectance spectra of outer solar system surfaces is achieved by a variety of methods. These include matching spectral curves, matching spectral features, quantitative spectral interpretation, and theoretical modeling of spectra. All of these approaches rely upon laboratory measurements of one kind or another. The bulk of these laboratory measurements are obtained with the sample of interest at ambient temperatures and pressures. However, surface temperatures of planets, satellites, and asteroids in the outer solar system are significantly cooler than ambient laboratory conditions on Earth. The infrared spectra of many materials change as a function of temperature. As has been recently demonstrated it is important to assess what effects colder temperatures have on spectral properties and hence, compositional interpretations. Titan tholin is a solid residue created by energetic processing of H-, C-, and N-bearing gases. Such residues can also be created by energetic processing if the gases are condensed into ices. Titan tholin has been suggested as a coloring agent for several surfaces in the outer solar system. Here we report laboratory measurements of Titan tholin at a temperature of 100 K and compare these to measurements of the same sample near room temperature. At low temperature the absorption features beyond 1 micrometer narrow slightly. At wavelengths greater than approx. 0.8 micrometer the overall reflectance of the sample decreases slightly making the sample less red at low temperatures. We will discuss the implications of the laboratory measurements for interpretation of cold outer solar system surfaces.

Roush, T. L.↗
DOE OSTI2024

Competing Radical and Molecular Channels in the Unimolecular Dissociation of Methylformate

The thermal dissociation of methylformate has been characterized by numerous experimental and theoretical studies that all seem to agree that the lowest energetically accessible process is a 3-center H-atom transfer that leads to the molecular products CH3OH 3 OH + CO. However, these literature studies seem to be at odds with regards to the role of other competing molecular eliminations and bond-fission processes and therefore a complete and resolved mechanistic picture of methylformate thermal dissociation still eludes us. In this work, we have performed high-level electronic structure theory calculations to characterize the energetics of other overlooked molecular and radical processes that can originate on the complex CH3OCHO 3 OCHO potential energy surface (PES). The present calculations do indeed confirm that the lowest energy process accessible on this PES is molecular elimination to form CH3OH 3 OH + CO. However, unlike prior theoretical studies, the present calculations reveal that the second lowest energy process is a 5-center concerted elimination process that leads to the direct formation of H2 2 + CH2O 2 O + CO. We also note that HCO2 2 from the lowest-lying bond fission has two energetically comparable electronic states (of 2 B 2 and 2 A 1 symmetry). Furthermore, the barrier for H-atom migration of CH3OCHO 3 OCHO to form the carbene (CH3OCOH) 3 OCOH) is similar to that for the direct 4-center elimination process leading to CH2O 2 O + CH2O 2 O characterized in prior literature studies. Radical and molecular pathways to CH3 3 + HOCO and CH4 4 + CO2 2 can also be facilitated from this carbene. Master equation calculations were performed to characterize the competition between the various molecular and radical processes on this more elaborate CH3OCHO 3 OCHO PES. The results of the present theoretical analyses were used to resolve outstanding questions on the role of secondary radical- initiated reactions in characterizing prior literature experimental studies.

Chemical Kinetics↗
NASA NTRSDate not supplied

Assessment of a Surface Propellant Transportation System Concept for Operations on Mars

NASA is working to define the architecture needed for a Mars exploration campaign. One potential architecture option allows for pre-deployment of essential cargo and equipment to support a crew landing, including the pre-positioning of a Mars Ascent Vehicle (MAV). This MAV is likely to represent the largest single payload that must be landed on the Martian surface. Its size would be influenced by the amount of mass that state-of-the-art Entry, Descent, and Landing (EDL) systems would be capable of placing on Mars. One possible method of increasing the usable size of the MAV without exceeding available EDL capabilities is to land the MAV without its ascent propellant on board. Following such a method may necessitate a strategy to acquire sufficient ascent propellant to allow a crew to safely depart the Martian surface. This presentation describes a conceptual return propellant strategy that uses a liquid transportation skid, or pallet, to be used in conjunction with a rover mobility system to transfer cryogenic propellant, consisting of oxygen and methane, across the Martian surface from a delivery lander to the MAV to enable its launch. Design considerations, concept of operations, and rover energetics will be discussed in this presentation.

Surface↗
NASA NTRSDate not supplied

Assessment of a Surface Propellant Transportation System Concept for Operations on Mars

NASA is working to define the architecture needed for a Mars exploration campaign. One potential architecture option allows for pre-deployment of essential cargo and equipment to support a crew landing, including the pre-positioning of a Mars Ascent Vehicle (MAV). This MAV is likely to represent the largest single payload that must be landed on the Martian surface. Its size would be influenced by the amount of mass that state-of-the-art Entry, Descent, and Landing (EDL) systems would be capable of placing on Mars. One possible method of increasing the usable size of the MAV without exceeding available EDL capabilities is to land the MAV without its ascent propellant on board. Following such a method may necessitate a strategy to acquire sufficient ascent propellant to allow a crew to safely depart the Martian surface. This paper describes a conceptual return propellant strategy that uses a liquid transportation skid, or pallet, to be used in conjunction with a rover mobility system to transfer cryogenic propellant, consisting of oxygen and methane, across the Martian surface from a delivery lander to the MAV to enable its launch. Design considerations, concept of operations, and rover energetics will be discussed in this paper.

Propellant↗
DOE OSTI2020

Controlling Metal–Organic Framework/ZnO Heterostructure Kinetics through Selective Ligand Binding to ZnO Surface Steps

Metal–organic framework (MOF) heterostructures exhibit unique properties beyond those of individual components, but their design requires an understanding of energetic and kinetic controls at MOF–substrate interfaces. Although the structural relationship has been widely used in heterostructure design, it overlooks the interplay between the organic ligand and the substrate which controls the kinetics and energetics of growth of the final structure. In this study, we used zeolitic imidazolate frameworks (ZIF-8) on ZnO as a model system to evaluate this interplay via in situ monitoring and simulations. Our results demonstrate multiple roles of the 2-methyl-imidazole (2-MIM) ligand as “dissolution-promoter”, “step-pinner”, and “terrace-binder” on the ZnO (001) face and “dissolution-promoter” and “terrace-binder” on the ZnO (100) face. Through these multiple face-specific roles, 2-MIM modulates ZnO dissolution kinetics and, hence, the Zn 2+ release rate, tuning local supersaturations that dictating the characteristic ZIF-8 crystallization kinetics on different substrate faces. The critical thickness for transition from 2D to 3D growth is dictated by competition between interfacial and strain energies. The atomic-scale mechanism of the coupled substrate dissolution and MOF growth, mediated by selective linker–substrate binding, furnishes a new synthesis pathway for other complex heterostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Do Impulsive Solar-Energetic-Electron (SEE) Events Drive High-Voltage Charging Events on the Nightside of the Moon?

When the Earth’s moon is in the supersonic solar wind, the darkside of the Moon and the lunar plasma wake can be very dangerous charging environments. In the absence of photoelectron emission (dark) and in the absence of cool plasma (wake), the emission or collection of charge to reduce electrical potentials is difficult. Unique extreme charging events may occur during impulsive solar-energetic-electron (SEE) events when the lunar wake is dominated by relativistic electrons, with the potential to charge and differentially charge objects on and above the lunar surface to very-high negative electrical potentials. In this report the geometry of the magnetic connections from the Sun to the lunar nightside are explored; these magnetic connections are the pathways for SEEs from the Sun. Rudimentary charging calculations for objects in the relativistic-electron environment of the lunar wake are performed. To enable these charging calculations, secondary-electron yields for impacts by relativistic electrons are derived. Needed lunar electrical-grounding precautions for SEE events are discussed. Calls are made 1) for future dynamic simulations of the plasma wake in the presence of time-varying SEE-event relativistic electrons and time-varying solar-wind magnetic-field orientations and 2) for future charging calculations in the relativistic-electron wake environment and on the darkside lunar surface.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

AugerPrime surface detector electronics

Operating since 2004, the Pierre Auger Observatory has led to major advances in our understanding of the ultra-high-energy cosmic rays. The latest findings have revealed new insights that led to the upgrade of the Observatory, with the primary goal of obtaining information on the primary mass of the most energetic cosmic rays on a shower-by-shower basis. In the framework of the upgrade, called AugerPrime, the 1660 water-Cherenkov detectors of the surface array are equipped with plastic scintillators and radio antennas, allowing us to enhance the composition sensitivity. To accommodate new detectors and to increase experimental capabilities, the electronics is also upgraded. This includes better timing with up-to-date GPS receivers, higher sampling frequency, increased dynamic range, and more powerful local processing of the data. In this paper, the design characteristics of the new electronics and the enhanced dynamic range will be described. The manufacturing and test processes will be outlined and the test results will be discussed. The calibration of the SD detector and various performance parameters obtained from the analysis of the first commissioning data will also be presented.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
NASA NTRS2023

Formation of Amino Acids and Carboxylic Acids in Weakly Reducing Planetary Atmospheres by Solar Energetic Particles from the Young Sun

Life most likely started during the Hadean Eon; however, the environmental conditions which contributed to the complexity of its chemistry are poorly known. A better understanding of various environmental conditions, including global (heliospheric) and local (atmospheric, surface, and oceanic), along with the internal dynamic conditions of the early Earth, are required to understand the onset of abiogenesis. Herein, we examine the contributions of galactic cosmic rays (GCRs) and solar energetic particles (SEPs) associated with superflares from the young Sun to the formation of amino acids and carboxylic acids in weakly reduced gas mixtures representing the early Earth’s atmosphere. We also compare the products with those introduced by lightning events and solar ultraviolet light (UV). In a series of laboratory experiments, we detected and characterized the formation of amino acids and carboxylic acids via proton irradiation of a mixture of carbon dioxide, methane, nitrogen, and water in various mixing ratios. These experiments show the detection of amino acids after acid hydrolysis when 0.5% (v/v) of initial methane was introduced to the gas mixture. In the set of experiments with spark discharges (simulation of lightning flashes) performed for the same gas mixture, we found that at least 15% methane was required to detect the formation of amino acids, and no amino acids were detected in experiments via UV irradiation, even when 50% methane was used. Carboxylic acids were formed in non-reducing gas mixtures (0% methane) by proton irradiation and spark discharges. Hence, we suggest that GCRs and SEP events from the young Sun represent the most effective energy sources for the prebiotic formation of biologically important organic compounds from weakly reducing atmospheres. Since the energy flux of space weather, which generated frequent SEPs from the young Sun in the first 600 million years after the birth of the solar system, was expected to be much greater than that of GCRs, we conclude that SEP-driven energetic protons are the most promising energy sources for the prebiotic production of bioorganic compounds in the atmosphere of the Hadean Earth.

Kensei Kobayashi↗
DOE OSTI2022

An Energetic Diagnostic of Tropical Cyclone Size in f –Plane Simulations

As a major feature of tropical cyclones (TCs), controlling factors of TC outer size or size scaling remains a fundamental scientific question. The Rossby deformation radius and a natural extent associated with potential intensity have been proposed as two scalings of TC size. But neither of them satisfactorily captures the sensitivity of TC size to sea surface temperature (SST) in idealized f-plane simulations. Inspired by the studies of the Hadley circulation, here we proposed a new TC scaling based on an energetic diagnostic scaling. TC size is primarily a ratio of the secondary circulation strength to subsidence velocity, further determined by the total atmospheric heating in the ascending area, the gross moist stability, the diabatic cooling, and the dry static stability. The former two is based on the moist energetic budget applied to the whole storm structure, while the latter two is based on the dry thermodynamic budget applied to the subsidence areas. The new scaling well captured the sensitivity of TC size to SST in idealized f-plane simulations, partly resulted from expanded ascending area, increased surface moisture deficit, and weakened subsidence with increased SST.

58 GEOSCIENCES↗
DOE OSTI2023

A Coverage Self-Consistent Microkinetic Model for Vapor-Phase Formic Acid Decomposition over Pd/C Catalysts

An iterative approach utilizing density functional theory (DFT, PW91-GGA)-informed mean-field microkinetic models and reaction kinetics experiments is used to determine the reaction mechanism and the active site for formic acid (HCOOH, FA) decomposition over a Pd/C catalyst. Models parametrized using DFT energetics on clean Pd(100) and Pd(111) required large corrections to the DFT energetics for capturing our experimental data. Further, both Pd(111) and Pd(100) models predicted a high coverage of adsorbed CO (CO*), inconsistent with the assumption of a clean surface at which the rate parameters for these models were calculated. To better represent the active site under reaction conditions and explicitly account for the presence of CO*, subsequent microkinetic models were formulated using DFT energetics that were calculated on partially (5/9 ML) CO*-covered Pd (111) and (100) facets. Upon parameter adjustment, the resultant 5/9 ML CO*-covered Pd(100) model, although consistent in terms of CO* coverage, was unable to capture the dehydration path measured in the experiments and was, therefore, deemed not to offer an accurate representation of the active site for FA decomposition over Pd/C. In contrast, a partially CO*-covered Pd(111) model was better at representing the catalytic active site, as in addition to being consistent in terms of CO* coverages, it required small adjustments of the DFT parameters to accurately capture the experimental data set (both dehydrogenation and dehydration). Our results suggest that the reaction occurs via the spectroscopically elusive carboxyl (COOH*) intermediate and that spectator CO*-assisted decomposition pathways play an important role under typical experimental conditions. In addition, our study highlights the importance of striving for coverage self-consistent microkinetic models and for including spectator-assisted mechanisms in order to develop an improved picture of the active site under reaction conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗