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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Ab initio-informed maximum entropy modeling of rovibrational relaxation and state-specific dissociation with application to the O{sub 2} + O system

Quasi-classical trajectory (QCT) calculations are used to study state-specific ro-vibrational energy exchange and dissociation in the O{sub 2} + O system. Atom-diatom collisions with energy between 0.1 and 20 eV are calculated with a double many body expansion potential energy surface by Varandas and Pais [Mol. Phys. 65, 843 (1988)]. Inelastic collisions favor mono-quantum vibrational transitions at translational energies above 1.3 eV although multi-quantum transitions are also important. Post-collision vibrational favoring decreases first exponentially and then linearly as Δv increases. Vibrationally elastic collisions (Δv = 0) favor small ΔJ transitions while vibrationally inelastic collisions have equilibrium post-collision rotational distributions. Dissociation exhibits both vibrational and rotational favoring. New vibrational-translational (VT), vibrational-rotational-translational (VRT) energy exchange, and dissociation models are developed based on QCT observations and maximum entropy considerations. Full set of parameters for state-to-state modeling of oxygen is presented. The VT energy exchange model describes 22 000 state-to-state vibrational cross sections using 11 parameters and reproduces vibrational relaxation rates within 30% in the 2500–20 000 K temperature range. The VRT model captures 80 × 10{sup 6} state-to-state ro-vibrational cross sections using 19 parameters and reproduces vibrational relaxation rates within 60% in the 5000–15 000 K temperature range. The developed dissociation model reproduces state-specific and equilibrium dissociation rates within 25% using just 48 parameters. The maximum entropy framework makes it feasible to upscale ab initio simulation to full nonequilibrium flow calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

The dissociative chemisorption of water on Ni(111): Mode- and bond-selective chemistry on metal surfaces

A fully quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of H{sub 2}O, HOD, and D{sub 2}O on Ni(111). For this late barrier system, excitation of both the bending and stretching modes significantly enhances dissociative sticking. The vibrational efficacies vary somewhat from mode-to-mode but are all relatively close to one, in contrast to methane dissociation, where the behavior is less statistical. Similar to methane dissociation, the motion of lattice atoms near the dissociating molecule can significantly modify the height of the barrier to dissociation, leading to a strong variation in dissociative sticking with substrate temperature. Given a rescaling of the barrier height, our results are in reasonable agreement with measurements of the dissociative sticking of D{sub 2}O on Ni(111), for both laser-excited molecules with one or two quanta of excitation in the antisymmetric stretch and in the absence of laser excitation. Even without laser excitation, the beam contains vibrationally excited molecules populated at the experimental source temperature, and these make significant contributions to the sticking probability. At high collision energies, above the adiabatic barrier heights, our results correlate with these barrier heights and mode softening effects. At lower energies, dissociative sticking occurs primarily via vibrationally nonadiabatic pathways. We find a preference for O–H over O–D bond cleavage for ground state HOD molecules at all but the highest collision energies, and excitation of the O–H stretch gives close to 100% O–H selectivity at lower energies. Excitation of the O–D stretch gives a lower O–D cleavage selectivity, as the interaction with the surface leads to energy transfer from the O–D stretch into the O–H bond, when mode softening makes these vibrations nearly degenerate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Generalized adsorption isotherms for molecular and dissociative adsorption of a polar molecular species on two polar surface geometries: Perovskite (100) (Pm-3m) and fluorite (111) (Fm-3m)

Lattice based kinetic Monte Carlo simulations have been used to determine a functional form for the second order adsorption isotherms on two commonly investigated crystal surfaces: the (111) fluorite surface and the (100) perovskite surface which has the same geometric symmetry as the NaCl (100) surface. The functional form is generalized to be applicable to all values of the equilibrium constant by a shift along the pressure axis. Functions have been determined for estimating the pressure at which a desired coverage would be achieved and, conversely, for estimating the coverage at a certain pressure. The generalized form has been calculated by investigating the surface adsorbate coverage across a range of thermodynamic equilibrium constants that span the range 10{sup −26} to 10{sup 13}. The equations have been shown to be general for any value of the adsorption equilibrium constant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Detection of Neutral CO Lost During Ionic Dissociation Using Atmospheric Pressure Thermal Dissociation Mass Spectrometry (APTD-MS)

Elucidation of ion dissociation patterns is particularly important to structural analysis by mass spectrometry (MS). However, typically, only the charged fragments from an ion dissociation event are detected in tandem MS experiments; neutrals are not identified. In recent years, we have developed an atmospheric pressure thermal dissociation (APTD) technique that can be applied to dissociate ions at atmosphere pressure and thus provide one way to characterize neutral fragments. In this paper, we focus on the detection of neutral CO resulting from amino acid and peptide ion dissociation. In the first set of experiments, several protonated amino acids (e.g., + 1 ion of phenylalanine) were found to undergo loss of a neutral (s) of total mass 46 Da, a process leading to iminium ion formation. We successfully detected the neutral species CO by using a CO sensor, UV-Vis and MS analysis following selective CO trapping with a rhodium complex. The capture of CO from dissociation of protonated amino acids supports the assignment of the loss of 46 Da to neutral losses of CO and H{sub 2}O, rather than loss of formaldehyde or dihydroxycarbene, other possible fragmentation pathways that have been subject of debate for a long time. In a second experiment, we used the APTD method in combination with the CO detection technique, to demonstrate the formation of CO in the conversion of b ions to a ions during peptide ion dissociations. These results showed the potential of APTD in the elucidation of ion dissociation mechanisms, using simple home-built apparatus. .

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2017

Evaluating Transport Properties and Ionic Dissociation of LiPF 6 in Concentrated Electrolyte

The presence of lithium hexafluorophosphate (LiPF 6 ) ion pairs in carbonate-based electrolyte solutions is widely accepted in the field of battery electrolyte research and is expected to affect solution transport properties. No existing techniques are capable of directly quantifying salt dissociation in these solutions. Previous publications by others have provided estimates of dissociation degrees using dilute solution theory and pulsed field gradient nuclear magnetic resonance spectroscopy (PFG-NMR) measurements of self-diffusivity. However, the behavior of a concentrated electrolyte solution can deviate significantly from dilute solution theory predictions. This paper, for the first time, instead uses Onsager–Stefan–Maxwell concentrated solution theory and the generalized Darken relation with PFG-NMR measurements to quantify the degrees of dissociation in electrolyte solutions (LiPF 6 in ethylene carbonate/diethyl carbonate, 1:1 by weight). At LiPF 6 concentrations ranging from 0.1 M to 1.5 M, the salt dissociation degree is found to range from 61% to 37%. Finally, transport properties are then calculated through concentrated solution theory with corrections for these significant levels of ion pairing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Dissociative Chemisorption and Oxidation of H 2 on the Stoichiometric IrO 2 (110) Surface

In this work, we investigated the dissociative chemisorption and oxidation of H 2 and D 2 on the stoichiometric IrO 2 (110) surface (“s-IrO 2 (110)”) using temperature programmed reaction spectroscopy (TPRS) and density functional theory (DFT) calculations. We find that the dissociative chemisorption of hydrogen occurs efficiently on s-IrO 2 (110) during adsorption at 90 K, with ~90% of the dissociated H 2 oxidizing to H 2 O during TPRS and evolving in a broad feature between 400 and 800 K. We also observe small quantities of H 2 desorbing in TPRS peaks at 200 K and 530 K, and show that these peaks arise from the desorption of molecularly-adsorbed H 2 and the recombination of atomic hydrogen, respectively. Our results demonstrate that H 2 dissociation on s-IrO 2 (110) occurs by a precursor-mediated mechanism wherein H 2 molecules adsorb strongly on coordinatively-unsaturated Ir atoms (Ircus) and the resulting σ-complexes then serve as precursors for H 2 bond cleavage. Our DFT calculations predict that H 2 adsorbs strongly on an atop-Ircus site, and that the H 2 complex can dissociate by a facile pathway involving H-transfer to a neighboring bridging O atom (Obr) to produce an H-Ircus/HObr pair. For this pathway, we predict that the energy barrier for dissociation is ~65 kJ/mol lower than the binding energy of the adsorbed H 2 complex. We also find that the total hydrogen uptake on s-IrO 2 (110) saturates at an H 2 coverage of ~0.65 ML during adsorption at 90 K, and present evidence that this limited uptake results from a strong influence of HObr groups on H 2 sigma-complex formation. Finally, we used DFT to examine pathways for H 2 O formation on s-IrO 2 (110) and find that steps leading directly to H 2 O formation are energetically demanding and likely determine the overall rate of H 2 oxidation on s-IrO 2 (110).

Dissociative Chemisorption↗
DOE OSTI2021

Ring Opening in Cycloheptane and Dissociation of 1-Heptene at High Temperatures

Cycloalkanes and alkenes are important components of real fuels but there is little kinetic and mechanistic data on the dissociation of most large cyclic and olefinic molecules at elevated temperatures. We present here the first experimental and theoretical investigation of dissociation of cycloheptane and the initial product from ring opening, 1-heptene. Experiments were performed in a diaphragmless shock tube using laser schlieren densitometry. Pyrolysis of cycloheptane (0.5-4% in Kr) was studied over 1450-2000 K and 30-120 Torr. Experiments with 1-heptene (1-4% in Kr) covered 1200-1650 K and 30-120 Torr. A newly developed chemical kinetic mechanism for pyrolysis of cycloheptane and 1-heptene is presented herein. Simulations are in very good agreement with the experimental measurements. Rate coefficients for the initial ring-opening process in cycloheptane, k 1 , and dissociation of 1-heptene, k 2 , were determined from the experiments. Both k 1 and k 2 are in falloff, and the pressure and temperature dependencies were well reproduced by theoretical calculations allowing extrapolation to conditions beyond the scope of this work. These calculations yielded the following expressions for k 1 and k 2 with the uncertainties estimated as +/- 40% and +/- 50% respectively: k 1 , infinity = 5 . 94 & times; 10 17 exp ( & minus;44 T, 521 ) s & minus;1 and k 2 , infinity = 8 . 86 & times; 10 16 exp ( & minus;35 , 887 T ) s & minus;1 . The results of this study indicate that cycloheptane dissociates similarly to cyclopentane and cyclohexane, i.e. ring-opening via C -C scission to a diradical that rapidly isomerizes to a conjugate 1-alkene. The secondary chemistry is dominated by the dissociation products of the 1-alkenes i.e. allyl and n-alkyl radicals. Furthermore, rates of dissociation of the cycloalkanes are size dependent and k cyclopentane << k cyclohexane < k cycloheptane . (c) 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Chemical kinetics↗
DOE OSTI2024

ASMS 2024 Investigation of Uranyl Perchlorate Anion Complexes in the Gas Phase via Infrared Multiphoton Dissociation and Collision Induced Dissociation

Investigation of Uranyl Perchlorate Anion Complexes in the Gas Phase via Infrared Multiphoton Dissociation and Collision Induced Dissociation Brittany D. M. Hodges, Christopher A. Zarzana, JungSoo Kim, Jonathan Martens, and W. C. M. Berden Introduction (120 words max) Effects of electronic structure on chemical bonding and reactivity play critical roles shaping the chemical bonding and reactivity behaviors of heavy elements. Understanding the role of f electrons in bond formation between the actinide-series elements like uranium with other ligands is critical for solving technical challenges associated with these heavy elements, important to nuclear fuel cycles, efficient separations of rare earth metals, and understanding the chemistry of stored nuclear fuels and related environmental management sites. In this study, we further examine the interactions between uranyl and the perchlorate ion in order to understand the structures of these ions through the use of IRMPD. Here we report the IRMPD spectra of [UO2(ClO4)3]-, [UO3(ClO4)2]-, and a proposed transition state. Methods (120 word max) IRMPD spectra and CID spectra were acquired using a Bruker amaZon QIT/MS instrument at the Free-Electron Lasers for Infrared eXperiments (FELIX) laboratory at Radboud University. The FELIX QIT/MS is modified to allow for the high-intensity tunable IR beam from FELIX to be directed into the ion packet, resulting in multiphoton dissociation that is measured only when the IR frequency is in resonance with an adequately high absorption vibrational mode of the mass-selected complex. DFT geometry optimizations and frequency calculations using the Gaussian suite of programs were performed using B3LYP, TPSSh, and PBE0 level of theory with 6-31+G(d) basis for the O, C, H, and N atoms and the SDD basis set for U. The SDD basis set employs the Stuttgart/Dresden effective core potential. Preliminary Data or Plenary Speakers Abstract (300 words max) Metal ion clusters of uranyl perchlorate were formed via direct electrospray ionization. For each metal ligand complex of interest, the parent ion was isolated and collision induced dissociation fragmentation and Infrared Multiphoton Dissociation (IRMPD) fragmentation spectra were acquired. Results presented here are the first look at the IRMPD spectra of [UO3(ClO4)2]-, [UO2(ClO4)3]-. Structures were examined using Gaussian at different levels of theory B3LYP level of theory, TPPSh and PBE0 levels, to reflect the behaviors of uranium metal ligand complexes most accurately. In these structures, we identified an overlap between each of these uranyl stretches resulting in their largely being obscured by a perchlorate mode. The CID product spectra agree with similar structures reported by Groenewold for uranyl nitrate in 2006 (10.1021/ja058106n).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Active Thermochemical Tables: Sequential Bond Dissociation Enthalpies of Methane, Ethane, and Methanol and the Related Thermochemistry

Active Thermochemical Tables (ATcT) thermochemistry for the sequential bond dissociations of methane, ethane, and methanol systems were obtained by analyzing and solving a very large thermochemical network (TN). Values for all possible C–H, C–C, C–O, and O–H bond dissociation enthalpies at 298.15 K (BDE298) and bond dissociation energies at 0 K (D0) are presented. The corresponding ATcT standard gas-phase enthalpies of formation of the resulting CHn, n = 4–0 species (methane, methyl, methylene, methylidyne, and carbon atom), C2Hn, n = 6–0 species (ethane, ethyl, ethylene, ethylidene, vinyl, ethylidyne, acetylene, vinylidene, ethynyl, and ethynylene), and COHn, n = 4–0 species (methanol, hydroxymethyl, methoxy, formaldehyde, hydroxymethylene, formyl, isoformyl, and carbon monoxide) are also presented. The ATcT thermochemistry of carbon dioxide, water, hydroxyl, and carbon, oxygen, and hydrogen atoms is also included, together with the sequential BDEs of CO2 and H2O. The provenances of the ATcT enthalpies of formation, which are quite distributed and involve a large number of relevant determinations, are analyzed by variance decomposition and discussed in terms of principal contributions. The underlying reasons for periodic appearances of remarkably low and/or unusually high BDEs, alternating along the dissociation sequences, are analyzed and quantitatively rationalized. The present ATcT results are the most accurate thermochemical values currently available for these species.

Active Thermochemical Tables↗
DOE OSTI2017

Trends in homolytic bond dissociation energies of five- and six-coordinate hydrides of Group 9 transition metals: Co, Rh, Ir

The homolytic bond dissociation energies of a series of five- and six-coordinate monoand di-hydride complexes of the type HM(diphosphine)2 and [H2M(diphosphine)2]+ (where M = Co, Rh and Ir) are calculated and compared with experimental values. This work probes the relationship between the homolytic bond dissociation energies (HMBDEs) of these complexes in these two different coordination environments and formal oxidation states. The results of these calculations and previous experimental observations suggest that for M = Rh the HMBDE of the five-coordinate HM(diphosphine)2 species are 0-2 kcal/mol larger than the HMBDE of the corresponding six-coordinate [H2M(diphosphine)2]+ species. For M = Ir the bond energies of the fiveand six-coordinate complexes are nearly the same and for M = Co the six-coordinate species are 1-5 kcal/mol less than the corresponding five-coordinate species. Simplified models of large and complicated ligands seem to capture the essential trends and give very good estimates of these thermodynamic properties in such systems.

homolytic bond dissociation, metal hydrides, dipho↗
DOE OSTI2016

Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH{sub 4} on Pt(111)

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH{sub 4} dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v{sub 3} and 2v{sub 3}, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v{sub 1} symmetric stretch of CH{sub 4} is more effective at promoting the dissociative chemisorption of CH{sub 4} than exciting the 1v{sub 3} antisymmetric stretch. This behavior is explained in terms of symmetry, mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v{sub 3} state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. Our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

MULTI-WAVELENGTH OBSERVATIONS OF THE DISSOCIATIVE MERGER IN THE GALAXY CLUSTER CIZA J0107.7+5408

We present results based on X-ray, optical, and radio observations of the massive galaxy cluster CIZA J0107.7+5408. We find that this system is a post-core-passage, dissociative, binary merger, with the optical galaxy density peaks of each subcluster leading their associated X-ray emission peaks. This separation occurs because the diffuse gas experiences ram pressure forces, while the effectively collisionless galaxies (and presumably their associated dark matter (DM) halos) do not. This system contains double-peaked diffuse radio emission, possibly a double radio relic with the relics lying along the merger axis and also leading the X-ray cores. We find evidence for a temperature peak associated with the SW relic, likely created by the same merger shock that is powering the relic radio emission in this region. Thus, this system is a relatively rare, clean example of a dissociative binary merger, which can in principle be used to place constraints on the self-interaction cross-section of DM. Low-frequency radio observations reveal ultra-steep spectrum diffuse radio emission that is not correlated with the X-ray, optical, or high-frequency radio emission. We suggest that these sources are radio phoenixes, which are preexisting non-thermal particle populations that have been re-energized through adiabatic compression by the same merger shocks that power the radio relics. Finally, we place upper limits on inverse Compton emission from the SW radio relic.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Investigation of Uranyl Perchlorate Anion Complexes in the Gas Phase via Infrared Multiphoton Dissociation and Collision‐Induced Dissociation

The infrared multiphoton dissociation spectrum of the gas-phase uranyl perchlorate anion ([UO 2 (ClO 4 ) 3 ] − ) was measured. Here, the asymmetric uranyl stretch lies somewhere between 930 and 1030 cm −1 , though it could not be deconvoluted from a closely located perchlorate stretching mode. The experimentally measured spectrum was in good agreement with spectra calculated using density functional theory with the B3LYP and TPSSh functionals and Grimme's D3 dispersion corrections with Becke–Johnson damping. The calculations suggest that the asymmetric uranyl stretch lies in the range of 970–980 cm −1 , about 20–30 cm −1 higher than for the analogous uranyl trinitrato complex and consistent with perchlorate as a weaker ligand than nitrate. Like the uranyl trinitrato anion, fragmentation of [UO 2 (ClO 4 ) 3 ] − by collision-induced dissociation resulted in loss of a ClO 3 • radical to form [UO 3 (ClO 4 ) 2 ] − . Infrared multiphoton dissociation measurements of [UO 3 (ClO 4 ) 2 ] − indicate that the structure of the product ion has an O − ligand bound to the uranyl in a T-arrangement and two perchlorate ligands, matching the findings from uranyl nitrato complexes. The uranyl stretch in this complex was slightly separated from the perchlorate modes and was measured at 906 cm −1 , slightly higher than for the analogous nitrate complex, again consistent with perchlorate as a weaker ligand than nitrate in the gas phase.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2022

Influence of Long-Range Forces on the Transition States and Dynamics of NaCl Ion-Pair Dissociation in Water

We study NaCl ion-pair dissociation in a dilute aqueous solution using computer simulations both for the full system with long-range Coulomb interactions and for a well-chosen reference system with short-range intermolecular interactions. Analyzing results using concepts from Local Molecular Field (LMF) theory and the recently proposed AI-based analysis tool “State predictive information bottleneck” (SPIB), we show that the system with short-range interactions can accurately reproduce the transition rate for the dissociation process, the dynamics for moving between the underlying metastable states, and the transition state ensemble. Contributions from long-range interactions can be largely neglected for these processes because long-range forces from the direct interionic Coulomb interactions are almost completely canceled (>90%) by those from solvent interactions over the length scale where the transition takes place. Thus, for this important monovalent ion-pair system, short-range forces alone are able to capture detailed consequences of the collective solvent motion, allowing the use of physically suggestive and computationally efficient short-range models for the dissociation event. Here, we believe that the framework here should be applicable to disentangling mechanisms for more complex processes such as multivalent ion disassociation, where previous work has suggested that long-range contributions may be more important.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Nonadiabatic Hydrogen Dissociation on Copper Nanoclusters

Copper surfaces display high catalytic selectivity but have poor hydrogen dissociation kinetics; therefore, we consider icosahedral Cu 13 nanoclusters to understand how nanoscale structure might improve catalytic prospects. We find that the spin state is a surprisingly important design consideration. Cu 13 clusters have large magnetic moments due to finite size and symmetry effects and exhibit magnetization-dependent catalytic behavior. The most favorable transition state for hydrogen dissociation has a lower activation energy than that on single-crystal copper surfaces but requires a magnetization switch from 5 to 3 μ B . Without this switch, the activation energy is higher than that on single-crystal surfaces. Weak spin–orbit coupling hinders this switch, decreasing the kinetic rate of hydrogen dissociation by a factor of 16. Here, we consider strategies to facilitate magnetization switches through optical excitations, substitution, charge states, and co-catalysts; these considerations demonstrate how control of magnetic properties could improve catalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗