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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Competing ionization and dissociation in the H 2 gerade system

A numerically solvable two-dimensional (2D) model, employed by the authors to study the dissociative recombination of H$^+_2$ in the ungerade symmetry, is extended to describe the collision process in the gerade symmetry of H$_2$. In this symmetry, the ionization and dissociation processes are driven primarily by the direct, curve-crossing mechanism. The model is represented by a set of three coupled electronic channels in 2D, in the space of $\textit{s, p, d}$ partial waves of the colliding electron. In this work, we demonstrate that the Born-Oppenheimer properties of the H$_2$ molecule in the relevant range of internuclear distances can be described by such a model. The molecular rotational degrees of freedom are accounted for by the rotational frame transformation. The numerical solution of the model is discussed, and the resulting rovibrationally inelastic and dissociative recombination cross sections are compared with the available data.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Dissociation slowdown by collective optical response under strong coupling conditions

We consider an ensemble of diatomic molecules resonantly coupled to an optical cavity under strong coupling conditions at normal incidence. Photodissociation dynamics is examined via direct numerical integration of the coupled Maxwell–Schrödinger equations with molecular rovibrational degrees of freedom explicitly taken into account. It is shown that the dissociation is significantly affected (slowed down) when the system is driven at its polaritonic frequencies. The observed effect is demonstrated to be of transient nature and has no classical analog. An intuitive explanation of the dissociation slowdown at polaritonic frequencies is proposed.

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

Predissociation-based measurements of bond dissociation energies: US 2 , OUS, and USe

The uranium-containing molecules US 2 , OUS, and USe have been investigated using a pulsed laser ablation supersonic beam molecular source with time-of-flight mass spectrometric detection. Spectra have been recorded using the resonant two-photon ionization method over the spectroscopic range from 277 to 238 nm. These species have a myriad of excited electronic states in this spectroscopic region, leading to spectra that are highly congested and appear quasicontinuous. Sharp predissociation thresholds are observed, allowing precise bond dissociation energies to be measured. In the case of the triatomic molecules, it was necessary to use one laser for excitation and a delayed laser for ionization in order to observe a sharp predissociation threshold that allowed a precise bond dissociation energy to be measured. The resulting thermochemical values are D 0 (SU-S) = 4.910 ± 0.003 eV, D 0 (OU-S) = 5.035 ± 0.004 eV, and D 0 (USe) = 4.609 ± 0.009 eV. These results provide the first measurement of D 0 (USe) and reduce the error limits in the previous values of D 0 (SU-S) and D 0 (OU-S) by a factor of more than 70.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Resolving metal binding properties within subunits of a multimeric enzyme Mnx by surface induced dissociation and native ion mobility mass spectrometry

Multi-subunit enzymes function as coordinated assemblies. Yet most enzymatic assays measure the summed output of all populations in solution and cannot easily differentiate contributions of individual subunits. Native mass spectrometry detects intact protein complexes in the gas phase. Surface induced dissociation further releases subunits from protein complexes while retaining compact conformations and bound ligands. Combined with ion mobility, the released subunits can then be carefully monitored for more in-depth structural analysis. Mnx is a unique bacterial multicopper oxidase complex that oxidizes Mn(II) to form MnO 2 minerals, and is composed of three subunits: MnxG, a multicopper oxidase containing the active site, and two accessory proteins, MnxE and MnxF which also bind copper ions. Other known multicopper oxidases do not require accessory proteins, therefore the functions of MnxE and MnxF are not well understood. Here, we use native mass spectrometry with surface induced dissociation and ion mobility to characterize the metal binding properties of Mnx with two metals, catalytic Cu(II) and Mn(II) substrate. We demonstrate our assay can detect subtle structural changes within each subunit, which are presumably related to the allosteric mechanism. We also noticed that ionic strength and solution composition can impact metal binding and must be carefully investigated for such experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

High-Temperature Dissociation of Neopentanol: Shock Tube/Photoionization Mass Spectrometry Studies

Herein, the pyrolysis mechanism of 2,2-dimethylpropan-1-ol (neopentanol) has been investigated at high temperatures (1128–1401K) and high pressures (5 and 15 bar). The experiments were performed in a miniature shock tube coupled to a time-of-flight mass spectrometer. Cations were generated by tunable vacuum ultraviolet photoionization resulting in multidimensional data sets containing mass and photoionization spectra and the time histories of species. At the elevated temperatures and pressures of this work, neopentanol was determined to dissociate primarily by the scission of a C–C bond yielding tert-butyl and hydroxymethyl radicals. These promptly form isobutene and formaldehyde by H-atom elimination. In the structurally similar molecule neopentane, roaming radical reactions have previously been found to be important under conditions close to the present work (1260–1459 K, 1.1 bar). There are two possible roaming radical reactions for neopentanol. However, no experimental evidence for these reactions was found at the elevated pressures in this study, and the dissociation of neopentanol is dominated by bond scission yielding radical products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Photodissociation of H 2 on Ag and Au Nanoparticles: Effect of Size and Plasmon versus Interband Transitions on Threshold Intensities for Dissociation

This Article provides new insights concerning the simulation of plasmon-driven chemical reactions using real-time TDDFT based on the tight-binding electronic structure code DFTB+, with applications to the dissociation of H 2 on octahedral silver and gold nanoparticles with 19–489 atoms. A new component of these calculations involves sampling a 300 K canonical ensemble to determine the distribution of possible outcomes of the calculations, and with this approach we are able to determine the threshold for dissociation as a function of laser intensity, wavelength, and nanocluster size. We show that the threshold intensity varies as an inverse power of nanocluster size, which makes it possible to extrapolate the results to sizes that are more typical of experimental studies. The intensities obtained from this extrapolation are around a factor of 100 above powers used in the pulsed experiments. This is a closer comparison of theory and experiment than has been obtained in previous real-time simulations, and the remaining discrepancy can be understood in terms of electromagnetic hot spots that are associated with cluster formation. Here, we also compare the influence of plasmon excitation versus interband excitation on reaction thresholds, revealing that for silver clusters plasmon excitation leads to lower thresholds, but for gold clusters interband excitation is more effective. Our study also includes an analysis of charge transfer to and from the H 2 molecule, and a determination of orbital populations during and after the pulse, showing the correlation between metal excitations and the location of the antibonding level of H 2 .

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Facilitating Hydrogen Dissociation over Dilute Nanoporous Ti–Cu Catalysts

The dissociation of H 2 is an essential elementary step in many industrial chemical transformations, typically requiring precious metals. Here, we report a hierarchical nanoporous Cu catalyst doped with small amounts of Ti (npTiCu) that increases the rate of H 2 –D 2 exchange by approximately one order of magnitude compared to the undoped nanoporous Cu (npCu) catalyst. The promotional effect of Ti was measured via steady-state H 2 –D 2 exchange reaction experiments under atmospheric pressure flow conditions in the temperature range of 300–573 K. Pretreatment with flowing H 2 is required for stable catalytic performance, and two temperatures, 523 and 673 K, were investigated. The experimentally determined H 2 –D 2 exchange rate is 5–7 times greater for npTiCu vs the undoped Cu material under optimized pretreatment and reaction temperatures. The H 2 pretreatment leads to full reduction of Cu oxide and partial reduction of surface Ti oxide species present in the as-prepared catalyst as demonstrated using in situ ambient pressure X-ray photoelectron spectroscopy and X-ray absorption spectroscopy. The apparent activation energies and pre-exponential factors measured for H 2 –D 2 exchange are substantially different for Ti-doped vs undoped npCu catalysts. Density functional theory calculations suggest that isolated, metallic Ti atoms on the surface of the Cu host can act as the active surface sites for hydrogen recombination. Furthermore, the increase in the rate of exchange above that of pure Cu is caused primarily by a shift in the rate-determining step from dissociative adsorption on Cu to H/D atom recombination on Ti-doped Cu, with the corresponding decrease in activation entropy that it produces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Efficiency of charge transfer in changing the dissociation dynamics of OD + transients formed after the photo-fragmentation of D 2 O

Here, we present an investigation of the relaxation dynamics of deuterated water molecules after direct photo-double ionization at 61 eV. We focus on the very rare D + + O + + D reaction channel in which the sequential fragmentation mechanisms were found to dominate the dynamics. Aided by theory, the state-selective formation and breakup of the transient OD + (a 1 Δ, b 1 Σ + ) is traced, and the most likely dissociation path—OD + : a 1 Δ or b 1 Σ + → A 3 Π → X 3 Σ – → B 3 Σ – —involving a combination of spin–orbit and non-adiabatic charge transfer transitions is determined. The multi-step transition probability of this complex transition sequence in the intermediate fragment ion is directly evaluated as a function of the energy of the transient OD + above its lowest dissociation limit from the measured ratio of the D + + O + + D and competing D + + D + + O sequential fragmentation channels, which are measured simultaneously. Our coupled-channel time-dependent dynamics calculations reproduce the general trends of these multi-state relative transition rates toward the three-body fragmentation channels.

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

Importance of one- and two-photon transitions in the strong-field dissociation of NO 2+

Employing a coincidence three-dimensional momentum imaging technique, we investigate the ultrafast, intense laser-induced dissociation of a metastable NO 2+ ion beam into N + + O + . Based on the kinetic energy release and angular distributions, measured using both 774-nm and second-order-harmonic 387-nm pulses, we show that the main processes driving dissociation in pulses of about 10 14 W/cm 2 peak intensity are one- and two-photon transitions from the X 2 Σ + ground state to the A 2 Π first-excited state. First-order perturbation theory calculations also corroborate these findings.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

On the distribution of stacking faults at dissociated medium-angle grain boundaries: Crystallographic geometry and metastability

Grain boundaries in FCC metals with low stacking-fault energy can form in dissociated configurations of stacking faults. Perhaps the most studied example is 9R stacking at boundaries near Σ3{112}, where the distribution of stacking faults is related to the emission of Shockley partial dislocations. Here, we combine atomic-resolution electron microscopy, atomistic simulations, and dislocation theory to demonstrate that boundaries vicinal to Σ33a support the stabilization of dissociated 9R stacking within a narrow range of inclinations. This boundary is interesting since its misorientation (20.05°) lies in the medium-angle regime, just past the upper misorientation limit for low-angle boundaries, motivating questions for how best to describe it in terms of dislocations. Our HAADF-STEM observations of thin film bicrystals, supported by atomistic modeling, reveal that this inclination dependence arises from specific geometric constraints on the arrangement of Shockley partial dislocations at the interface. Quantification of stacking-fault distributions across multiple boundaries indicates that the density and spacing of faults closely follow the ideal 9R motif, with subtle variations reflecting the complex energy landscape of these boundaries. Through energetic analysis, we establish the presence of competing metastable states enabled by variations in stacking sequences, emphasizing the significant role of crystallographic geometry. We generalize our analysis as a function of misorientation, showing how 9R at the Σ33a boundary is related to previous observations and calculations of HCP at a 29.7° boundary. This study provides a crystallographically grounded framework connecting dislocation structures, stacking-fault distributions, and metastability at grain boundaries in FCC metals.

Atomistic modeling↗
DOE OSTI2025

Effect of dilute Rh on oxygen dissociation, spillover, and the oxidation of Cu across many orders of magnitude pressure

Knowledge of how trace amounts of more reactive metals influence the oxidation rate and mechanism of Cu surfaces is essential for developing strategies to optimize the performance of Cu-based catalysts. We find that the addition of 1% Rh to Cu(111) increases the initial O 2 dissociation rate by approximately 9-fold. CO poisoning experiments reveal that single Rh atoms activate O 2 and facilitate the spillover of atomic oxygen to Cu sites. Scanning tunneling microscopy (STM) and in situ X-ray photoelectron spectroscopy (XPS) support this mechanism, showing enhanced surface oxygen near Rh atoms. Here, a density functional theory (DFT)-based model demonstrates that Rh binds the O 2 precursor 0.15 eV more strongly than Cu(111) and lowers the O 2 dissociation barrier by 0.02 eV. Both single-crystal and nanoparticle experiments show that at low oxygen pressures, Rh enhances Cu oxidation, whereas at higher pressures, it inhibits deeper oxidation, as evidenced by in situ ultraviolet-visible (UV-vis) spectra.

36 MATERIALS SCIENCE↗
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↗
DOE OSTI2022

Electronic Spectroscopy and Dissociation Dynamics of Vinyl-Substituted Criegee Intermediates: 2-Butenal Oxide and Comparison with Methyl Vinyl Ketone Oxide and Methacrolein Oxide Isomers

The 2-butenal oxide Criegee intermediate [(CH 3 CH=CH)CHOO], an isomer of the four-carbon unsaturated Criegee intermediates derived from isoprene ozonolysis, is characterized on its first π * ←π electronic transition and by the resultant dissociation dynamics to O ( 1 D) + 2-butenal [(CH 3 CH=CH)CHO] products. The electronic spectrum of 2-butenal oxide under jet-cooled conditions is observed to be broad and unstructured with peak absorption at 373 nm, spanning to half maxima at 320 and 420 nm, and in good accord with the computed vertical excitation energies and absorption spectra obtained for its lowest energy conformers. The distribution of total kinetic energy released to products is ascertained through velocity map imaging of the O ( 1 D) products. About half of the available energy, deduced from the theoretically computed asymptotic energy, is accommodated as internal excitation of the 2-butenal fragment. A reduced impulsive model is introduced to interpret the photodissociation dynamics, which accounts for the geometric changes between 2-butenal oxide and the 2-butenal fragment, and vibrational activation of associated modes in the 2-butenal product. Application of the reduced impulsive model to the photodissociation of isomeric methyl vinyl ketone oxide reveals greater internal activation of the methyl vinyl ketone product arising from methyl internal rotation and rock, which is distinctly different than the dissociation dynamics of 2-butenal oxide or methacrolein oxide.

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

Thermodynamically Optimized Machine-Learned Reaction Coordinates for Hydrophobic Ligand Dissociation

Ligand unbinding is mediated by its free energy change, which has intertwined contributions from both energy and entropy. It is important, but not easy, to quantify their individual contributions to the free energy profile. We model hydrophobic ligand unbinding for two systems, a methane particle and a C 60 fullerene, both unbinding from hydrophobic pockets in all-atom water. Using a modified deep learning framework, we learn a thermodynamically optimized reaction coordinate to describe the hydrophobic ligand dissociation for both systems. Interpretation of these reaction coordinates reveals the roles of entropic and enthalpic forces as the ligand and pocket sizes change. In both cases, we observe that the free-energy barrier to unbinding is dominated by entropy considerations. Furthermore, the process of methane unbinding is driven by methane solvation, while fullerene unbinding is driven first by pocket wetting and then fullerene wetting. For both solutes, the direct importance of the distance from the binding pocket to the learned reaction coordinate is present, but low. Furthermore, our framework and subsequent feature important analysis thus give useful thermodynamic insight into hydrophobic ligand dissociation problems that are otherwise difficult to glean.

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

Mixed Molecular and Dissociative Water Adsorption on Hydroxylated TiO 2 (110): An Infrared Spectroscopy and Ab Initio Molecular Dynamics Study

For this work, we have investigated the structure and dynamics of water (D 2 O) adsorbed on TiO 2 (110) for coverages between 0 and 1 monolayer with infrared reflection absorption spectroscopy (IRAS) and ab initio molecular dynamics (AIMD) simulations. For D 2 O coverages as low as 0.4 monolayers (ML) on a hydroxylated surface, IR spectra typical of hydrogen-bonded chains of water molecules are observed. However, for D 2 O coverages ≥ 0.3 ML, a sharp, high frequency peak is also observed in the p-polarized spectra that is red-shifted relative to the bridging hydroxyl peak. This new peak is not observed for water adsorbed on an oxidized surface. Based on the AIMD simulations and comparisons with previous IR spectra for TiO 2 nanoparticles, the new peak is assigned to terminal hydroxyl groups produced by dissociative adsorption of some of the water on TiO 2 (110). The simulations indicate that water dissociation is related to the presence of defect electrons in the system, but not due to direct interactions between adsorbed water and bridging hydroxyls.

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

How Does Water Dissociation Work in Bipolar Membranes?

Bipolar membranes (BPMs) create counteracting spatial gradients of pH and electrostatic potential in electrochemical systems, enabling applications in pH regulation, electrocatalysis, and separations. At the polarized junction of a BPM the water dissociation (WD, 2H2O ⇌ H3O+ + OH-) reaction can be driven, but it remains poorly understood. In this Perspective, we integrate molecular insights from bulk-water autoionization and the associated field effects with continuum descriptions of BPM electrostatics and experimental WD kinetic analyses to describe possible mechanisms of voltage-driven WD. Pristine BPM junctions highlight both the limits of primarily electric-field-driven WD and the practical challenges of junction stability at extreme reverse bias. Introducing heterogeneous catalyst layers, commonly metal oxides and graphene oxides, accelerates WD by orders of magnitude through hypothesized coupled effects in which surface acid-base functionality and high-density hydroxyl sites mediate proton-transfer steps, and catalyst mobile electronic/ionic charges redistribute the junction electric potential drop to shape the local electric fields and reactive microenvironments. Kinetic analyses suggest two regimes of heterogeneous WD mechanism, including field-driven ordering of interfacial water and a Second-Wien-Effect dissociation-barrier lowering. We conclude by defining the key unknown variables (local pH, electrostatic potential, catalyst charge state and relationships among mechanisms) and outlining experimental and multiscale modeling strategies needed for predictive WD catalysis and for controlling related ion-transfer reactions.

Wu, Yifan↗
DOE OSTI2023

Revealing CO 2 dissociation pathways at vicinal copper (997) interfaces

Size- and shape-tailored copper (Cu) nanocrystals can offer vicinal planes for facile carbon dioxide (CO 2 ) activation. Despite extensive reactivity benchmarks, a correlation between CO 2 conversion and morphology structure has not yet been established at vicinal Cu interfaces. Herein, ambient pressure scanning tunneling microscopy reveals step-broken Cu nanocluster evolutions on the Cu(997) surface under 1 mbar CO 2 (g). The CO 2 dissociation reaction produces carbon monoxide (CO) adsorbate and atomic oxygen (O) at Cu step-edges, inducing complicated restructuring of the Cu atoms to compensate for increased surface chemical potential energy at ambient pressure. The CO molecules bound at under-coordinated Cu atoms contribute to the reversible Cu clustering with the pressure gap effect, whereas the dissociated oxygen leads to irreversible Cu faceting geometries. Synchrotron-based ambient pressure X-ray photoelectron spectroscopy identifies the chemical binding energy changes in CO-Cu complexes, which proves the characterized real-space evidence for the step-broken Cu nanoclusters under CO(g) environments. Our in situ surface observations provide a more realistic insight into Cu nanocatalyst designs for efficient CO 2 conversion to renewable energy sources during C 1 chemical reactions.

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

Dissociative electron attachment to 5-bromo-uracil: non-adiabatic dynamics on complex-valued potential energy surfaces

Electron induced dissociation reactions are relevant to many fields, ranging from prebiotic chemistry to cancer treatments. However, the simulation of dissociation electron attachment (DEA) dynamics is very challenging because the auto-ionization widths of the transient negative ions must be accounted for. We propose an adaptation of the ab initio multiple spawning (AIMS) method for complex-valued potential energy surfaces, along the lines of recent developments based on surface hopping dynamics. Our approach combines models for the energy dependence of the auto-ionization widths, obtained from scattering calculations, with survival probabilities computed for the trajectory basis functions employed in the AIMS dynamics. The method is applied to simulate the DEA dynamics of 5-bromouracil in full dimensionality, i.e., taking all the vibrational modes into consideration. The propagation starts on the $π_{2}^{*}$ resonance state and describes the formation of Br - anions mediated by non-adiabatic couplings. The potential energies, gradients and non-adiabatic couplings were computed with the fractional-occupancy molecular orbital complete-active-space configuration-interaction method, and the calculated DEA cross section are consistent with the observed DEA intensities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗