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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 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Tracking ion intercalation into layered Ti 3 C 2 MXene films across length scales

Enhancing the energy stored and power delivered by layered materials relies strongly on improved understanding of the intricate interplay of electrolyte ions, solvents, and electrode interactions as well as the role of confinement. Here we report a highly integrated study with multiscale theory/modelling and experiments to track the intercalation of aqueous Li + , Na + , K + , Cs + , and Mg 2+ ions into Ti 3 C 2 MXene. The integrated analysis of experiments assisted by theory/modelling allows for a deep understanding of energy storage processes highlighting the importance of the dynamics of cations, their positionings between MXene sheets, their effects on mechanical properties and capacitive energy storage. Computational simulations and operando calorimetry measurements prove the processes involving cation dehydration and H+ rehydration, showing a good correlation for heat variations between experiments and theory. Operando liquid AFM mapped energy dissipation of ions appears non-uniformly across the MXene surface, indicating heterogeneities of ions inside the MXene and confirming partially the ion behaviour obtained in theory. We directly demonstrate that the average distance between the cation and MXene surface follows a modified two-sided Helmholtz model when plotted versus the open circuit potential capacitance, revealing a different electrical double layer mechanism in confinement. This new fundamental understanding lays the foundation for improved functional devices utilizing electrodes and membranes made of two-dimensional materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Unusual electrical conductivity driven by localized stoichiometry modification at vertical epitaxial interfaces

Precise control of lattice mismatch accommodation and interfacial cation diffusion is critical to modulate correlated functionalities in epitaxial heterostructures, particularly when the interface composition is positioned near a compositional phase transition boundary. Here we select La 1-x Sr x MnO 3 (LSMO) as a prototype phase transition oxide and establish vertical epitaxial interfaces with NiO for exploring the strong interplay between strain accommodation, stoichiometry modification, and localized electron transport across the interface. It is found that localized stoichiometry modification overcomes the dead layer problem plaguing LSMO and leads to strongly directional conductivity, as manifested by a more than three orders of magnitude difference between out-of-plane and in-plane conductivity. Comprehensive atomic scale structural characterization and transport measurements reveal that this emerging behavior is created by a compositional change produced by preferential cation diffusion that pushes the LSMO phase transition from insulating into metallic within an ultrathin interface region. This study explores the nature of unusual electrical conductivity at vertical epitaxial interfaces and highlights the beneficial role of controllable cation diffusion that enables emerging functionalities for a broad range of potential applications such as memristors, spintronic devices, and novel nanoelectronic devices using strongly correlated materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Mechanistic insight of KBiQ 2 (Q = S, Se) using panoramic synthesis towards synthesis-by-design

Solid-state synthesis has historically focused on reactants and end products; however, knowledge of reaction pathways, intermediate phases and their formation may provide mechanistic insight of solid-state reactions. With an increased understanding of reaction progressions, design principles can be deduced, affording more predictive power in materials synthesis. In pursuit of this goal, in situ powder X-ray diffraction is employed to observe crystalline phase evolution over the course of the reaction, thereby constructing a “panoramic” view of the reaction from beginning to end. We conducted in situ diffraction studies in the K–Bi–Q (Q = S, Se) system to understand the formation of phases occurring in this system in the course of their reactions. Powder mixtures of K 2 Q to Bi 2 Q 3 in 1:1 and 1.5:1 ratios were heated to 800 °C or 650 °C, while simultaneously collecting diffraction data. Three new phases, K 3 BiS 3 , β-KBiS 2 , and β-KBiSe 2 , were discovered. Panoramic synthesis showed that K 3 BiQ 3 serves an important mechanistic role as a structural intermediate in both chalcogen systems (Q = S, Se) in the path to form the KBiQ 2 structure. Thermal analysis and calculations at the density functional theory (DFT) level show that the cation-ordered β-KBiQ 2 polymorphs are the thermodynamically stable phase in this compositional space, while Pair Distribution Function (PDF) analysis shows that all α-KBiQ 2 structures have local disorder due to stereochemically active lone pair expression of the bismuth atoms. The formation of the β-KBiQ 2 structures, both of which crystallize in the α-NaFeO 2 structure type, show a boundary where the structure can be disordered or ordered with regards to the alkali metal and bismuth. A cation radius tolerance for six-coordinate cation site sharing of ($\frac{r^+}{r^{3+}}$) ~ 1.3 is proposed. The mechanistic insight the panoramic synthesis technique provides in the K–Bi–Q system is progress towards the overarching goal of synthesis-by-design.

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

Influence of Hydrogen and Oxygen on the Structure and Properties of Sputtered Magnesium Zirconium Oxynitride Thin Films

Nitride materials with mixed ionic and covalent bonding character and resulting good charge transport properties are attractive for optoelectronic devices. Recently, Mg-based ternary nitride materials were found to have large dielectric constants and high absorption coefficients with bandgaps appropriate for photovoltaic applications. However, their degenerate carrier concentrations still hinder their possible applications in solar cells and related optoelectronic devices. Therefore, further understanding and engineering of the parameters controlling the material properties of these ternary nitrides is highly desirable. In this paper we report that the structural, optical and electrical properties of magnesium zirconium oxynitride (MZNO) thin films synthesized by combinatorial sputtering with a wide range of cation compositions can be affected by incorporation of oxygen and hydrogen. Excess oxygen improved the crystallinity of MZNO thin films whereas hydrogen attracted oxygen and formed Mg-rich oxide layers at the grain boundaries which in turn reduced the conductivity. On the other hand, optical properties are more sensitive to the composition – both cation and anion ratios – rather than the presence of hydrogen. Compared to cation-stoichiometric MZNO (10 19 –10 20 cm -3 ), substantial reduction of carrier concentration down to ~10 14 cm -3 was achieved under Mg-rich conditions by supplying hydrogen during growth. Photoluminescence measurements showed that the films prepared with hydrogen were optoelectronically active. Overall, this study demonstrates that the material properties of MZN thin films can be significantly influenced by incorporation of oxygen and hydrogen.

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

Synthesis, modular composition, and electrochemical properties of lamellar iron sulfides

Transition metal chalcogenides with layered structures are promising materials for energy storage, catalysis, and electronics, among other areas. We have identified a new layered phase of iron sulfide containing interlayer solvated cations. We present an optimized synthesis for the Li + -containing material from an Fe(III) xanthate complex. Structure and composition data indicate the material consists of poorly-ordered iron sulfide layers separated by solvated cations. The lamellar spacing in these materials can be tuned by changing the identity of the cation. Furthermore, the lamellar spacing can also be reversibly tuned by the degree of solvation of the material. The material is electrically conductive and can serve as a pseudocapacitor with comparable performance to commercial materials such as MnO 2 . Finally, these materials also show promise as lithium or sodium ion battery cathodes with good capacity and reversibility.

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

A new metric to control nucleation and grain size distribution in hybrid organic–inorganic perovskites by tuning the dielectric constant of the antisolvent

In perovskite research, there is a widely exploited but poorly explained phenomenon in which the addition of “antisolvents (ATS)” to precursor solutions results in higher-quality films. We explain the mechanism and driving force underlying an antisolvent-driven solvent extraction process. Density functional theory calculations uncover the defining effects of antisolvent choice on the extent of complexation between a lead salt and a methylammonium cation in solution. We experimentally validate the computational results using ultraviolet-visible spectroscopy and 207 Pb nuclear magnetic spectroscopy of methylammonium lead iodide solutions, containing both a processing solvent and an antisolvent. Furthermore, we uncover, and subsequently identify, the appearance of new species in solution as a result of the addition of the antisolvent. Furthermore, we observe that the choice of antisolvent has a substantial effect on the nature of the complexation of the methylammonium lead iodide (MAPbI 3 ) precursor species, whose origin we explain at an atomic level; specifically, the lower the dielectric of the antisolvent, the stronger the intermolecular binding energy between methylammonium cation (MA + ) cation and PbI 3 - plumbate, independent of the solvent or antisolvent interaction with the lead salt. Thin films were characterized using scanning electron microscopy; images of the films show how the addition of an antisolvent influences and, importantly, can be used to alter thin-film grain size. Grain size and distribution in thin films is reflected by the choice of antisolvent, promoting slower nucleation rates, a lower nucleation density, and hence larger final grain size.

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

Observation of pressure-induced electron transfer in SnC 2 O 4

We examined the high pressure behavior of stannous oxalate via Raman and X-ray absorption spectroscopy (XAS) inside a diamond anvil cell. Phase transitions were observed to occur near 2.6 and 15 GPa which were reversible upon decompression to ambient conditions. When further pressurized above 15 GPa, the colorless material sustains irreversible chemical alterations and becomes bright red colored – darkening at higher pressures. Another irreversible phase transition occurred above 20 GPa. Concomitant with color change of the sample, we observed a softening of the ν(C–C) modes of the C 2 O 4 2- anion via Raman spectroscopy. We performed a separate XAS experiment which indicates that the Sn 2+ cation undergoes a partial reduction of the 2+ oxidation state with pressure which persists when the sample was depressurized to ambient conditions. Thus, electron density within the C–C bond in the oxalate anion appears to migrate toward the tin cation with pressure. This observation suggests that pressure can offer a very controllable means to vary cation–anion and unit cell dimensions (and thus the electric interactions causing electron movement) and thus the pressure-induced synthesis of novel materials.

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

The efficacy of Lewis affinity scale metrics to represent solvent interactions with reagent salts in all-inorganic metal halide perovskite solutions

Solvents employed in the solution processing of metal halide perovskites are known to play a key role in defining the morphology and properties of the resulting thin film, and thus the performance of perovskite solar cell devices. Accurate metrics are needed that are capable of differentiating among candidates, finding solvents that adequately solubilize the various precursor species in solution and facilitate the nucleation and growth of these materials. Existing metrics such as the unsaturated Mayer bond order (UMBO) and the Gutmann donor number (DN) have been tested for lead iodide perovskite systems; but there has yet to be a comprehensive study on their transferability to lead-free perovskite solutions. Here, we use ab initio methods (density functional theory) and regression analysis tools to study the usefulness of DN and BF 3 affinity scales in this regard. We compared the relative effectiveness of these scales to describe interactions between solvents and BXn perovskite salts of lead (Pb 2+ ), tin (Sn 2+ and Sn 4+ ), germanium (Ge 2+ ), bismuth (Bi 3+ ), and antimony (Sb 3+ and Sb 5+ ). The DN proved to be a better representation than the BF 3 of such interactions, reflecting the closer similarity of these species to the “parent” SbCl 5 Lewis acid than to BF 3 . In addition, we have uncovered the usefulness of the lithium cation affinity metric (LCA) to describe the strength of interactions between solvents and A-site cations (e.g. Na + , K + , Rb + and Cs + ) in all-inorganic metal halide perovskite solutions. We find that the coordination strengths of solvents towards species in all-inorganic metal halide perovskite solutions are best described by two different metrics with distinct modes of action: DN differentiates among BX n salt complexes, and LCA among A-site cation species. This revelation can help guide the choice of solvent to optimize processing conditions. It also emphasizes the importance of selecting solvents whose DN and LCA optimize coordination to key Lewis acid species in all-inorganic perovskite solutions.

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

Structural water in amorphous carbonate minerals: ab initio molecular dynamics simulations of X-ray pair distribution experiments

Water is known to play a controlling role in directing mineralization pathways and stabilizing metastable amorphous intermediates in hydrous carbonate mineral MCO 3 ·nH 2 O systems, where M 2+ is a divalent metal cation. Despite this recognition, the nature of the controls on crystallization is poorly understood, largely owing to the difficulty in characterizing the dynamically disordered structures of amorphous intermediates at the atomic scale. Here, we present a series of atomistic models, derived from ab initio molecular dynamics simulation, across a range of experimentally relevant cations (M = Ca, Mg, Sr) and hydration levels (0 ≤ n ≤ 2). Theoretical simulations of the dependence of the X-ray pair distribution function on the hydration level n show good agreement with available experimental data and thus provide further evidence for a lack of significant nanoscale structure in amorphous carbonates. Upon dehydration, the metal coordination number does not change significantly, but the relative extent of water dissociation increases, indicating that a thermodynamic driving force exists for water dissociation to accompany dehydration. Mg strongly favors monodentate conformation of carbonate ligands and shows a marked preference to exchange monodentate carbonate O for water O upon hydration, whereas Ca and Sr exchange mono- and bidentate carbonate ligands with comparable frequency. Finally, water forms an extensive hydrogen bond network among both water and carbonate groups that exhibits frequent proton transfers for all three cations considered suggesting that proton mobility is likely predominantly due to water dissociation and proton transfer reactions rather than molecular water diffusion.

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

Interplay of structural fluctuations and charge carrier dynamics is key for high performance of hybrid lead halide perovskites

The ability of methylammonium lead triiodide (MAPbI 3 ) to achieve photoelectric conversion efficiency that is on par with crystalline silicon has led to a surge of interest in perovskite photovoltaics. However, an in-depth understanding of how the ubiquitous coupling between the fast rovibrational movements of the organic cations and the phonon vibrations of the inorganic framework affects the relaxation and recombination of hot carriers remains largely elusive. Access to such knowledge is critical to guide design and increase efficiency of new classes of perovskite solar cells. In this report, we report a time-domain ab initio investigation of temperature dependent excited state dynamics in MAPbI 3 , with particular emphasis on nuclear anharmonic effects. The observed strong anharmonicity is attributed to softness of the material and unusual dynamical coupling between the organic and inorganic components. At an elevated temperature, the hydrogen bonding between MA and iodines is weakened, enhancing rotation of MA cations, which become more dynamically disordered. As a result, thermal vibrations of the inorganic Pb–I sublattice are suppressed, and the lattice anharmonicity is decreased. Thermal fluctuations of the electronic energy levels are found to follow the trend of anharmonic motions of Pb and I atoms, with holes relaxing faster to the band edges than electrons, due to higher density of the hole states. While elevated temperature accelerates intraband carrier cooling, it slows nonradiative carrier recombination. The latter result is important for performance, since solar cells and other devices heat up during operation. The reported signatures of coupled structural dynamics of the organic cations and inorganic framework unravel the interplay between anomalous structural fluctuations and charge carrier dynamics, which is of particular importance for fundamental understanding of the structure–property relationships in hybrid metal halide perovskites.

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

Coordination of copper within a crystalline carbon nitride and its catalytic reduction of CO 2

Inherently disordered structures of carbon nitrides have hindered an atomic level tunability and understanding of their catalytic reactivity. Starting from a crystalline carbon nitride, poly(triazine imide) or PTI/LiCl, the coordination of copper cations to its intralayer N-triazine groups was investigated using molten salt reactions. The reaction of PTI/LiCl within CuCl or eutectic KCl/CuCl 2 molten salt mixtures at 280 to 450 °C could be used to yield three partially disordered and ordered structures, wherein the Cu cations are found to coordinate within the intralayer cavities. Local structural differences and the copper content, i.e., whether full or partial occupancy of the intralayer cavity occurs, were found to be dependent on the reaction temperature and Cu-containing salt. Crystallites of Cu-coordinated PTI were also found to electrophoretically deposit from aqueous particle suspensions onto either graphite or FTO electrodes. As a result, electrocatalytic current densities for the reduction of CO 2 and H 2 O reached as high as ∼10 to 50 mA cm −2 , and remained stable for >2 days. Selectivity for the reduction of CO 2 to CO vs. H 2 increases for thinner crystals as well as for when two Cu cations coordinate within the intralayer cavities of PTI. Mechanistic calculations have also revealed the electrocatalytic activity for CO 2 reduction requires a smaller thermodynamic driving force with two neighboring Cu atoms per cavity as compared to a single Cu atom. These results thus establish a useful synthetic pathway to metal-coordination in a crystalline carbon nitride and show great potential for mediating stable CO 2 reduction at sizable current densities.

Chemistry↗
DOE OSTI2025

Cobalt–niobium co-doping of indium oxide: structural and adsorption/catalytic properties for CO 2 valorization

The co-doping of the indium oxide structure with cobalt and niobium is attempted using a microemulsion method to produce high-surface-area, mesoporous, functional materials. The co-doping leads to a major nanometric bixbyite oxide phase, with both cations occupying cation positions and affecting the size and shape of the oxide entities. For specific cobalt to niobium atomic ratios, the presence of a second surface phase is encountered. Such a surface phase corresponds to an ill-defined indium hydroxide-type phase. The coexistence of the two phases is a unique phenomenon associated with the presence of both cations, which play a decisive role in promoting the CO 2 adsorption capability of the solids, as well as the valorization of the molecule under dual heat–light excitation. The co-doping of indium oxide thus appears to be a unique way to intensify the analogous thermal (classical) catalytic process for the elimination/valorization of carbon dioxide.

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

Crystal structures and rotational dynamics of a two-dimensional metal halide perovskite (OA) 2 PbI 4

The extended charge carrier lifetime in metal halide perovskites is responsible for their excellent optoelectronic properties. Recent studies indicate that the superb device performance in these materials is intimately related to the organic cation dynamics. Here, we focus on the investigation of the two-dimensional hybrid perovskite, (C 8 H 17 NH 3 ) 2 PbI 4 (henceforth, OA + = C 8 H 17 NH 3 + ). Using elastic and quasielastic neutron scattering techniques and group theoretical analysis, we studied the structural phase transitions and rotational modes of the C 8 H 17 NH 3 + cation in (OA) 2 PbI 4 . Here, our results show that, in the high-temperature orthorhombic ( T > 310 K) phase, the OA + cation exhibits a combination of a twofold rotation of the NH 3 –CH 2 head group about the crystal c -axis with a characteristic relaxation time of ~6.2 ps, threefold rotations (C 3 ) of NH 3 and CH 3 terminal groups, and slow librations of the other atoms. Contrastingly, only the C 3 rotation is present in the intermediate-temperature orthorhombic (238 K < T < 310 K) and low-temperature monoclinic ( T < 238 K) phases.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Molecular polarizabilities as fingerprints of perturbations to water by ions and confinement

Perturbations to water, both by ions and confining media, have been the focus of numerous experimental and theoretical studies. Yet, several open questions remain, including the extent to which such perturbations modify the structural and dielectric properties of the liquid. Here, we present a first-principles molecular dynamics study of alkali cations in water (Li + , Na + , and K + ) as well as of water and LiCl and KCl solutions under confinement within carbon nanotubes (CNTs) of small diameter (1.1-1.5 nm). Our simulations support the view that the water structure is only modified locally in the presence of cations. We found that molecular polarizabilities are fingerprints of hydrogen bonding modifications, which occur at most up to the second solvation shell for all cations in bulk water. Under confinement, we found that the overall value of the molecular polarizability of water molecules near the surface is determined by the balance of two effects, which are quantitatively different in CNTs of different radii: the presence of broken hydrogen bonds at the surface leads to a decrease in the polarizabilities of water molecules, while the interaction with the CNT enhances polarizabilities. Interestingly, the reduction in dipole moments of interfacial water molecules under confinement is instead driven only by changes in the water structure and not by interfacial interactions. As expected, confinement effects on water molecular polarizabilities and dipole moments are more pronounced in the case of the 1.1 nm CNT.

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

Transformations to amorphous and X-type phases in swift heavy ion-irradiated Ln 2 O 3 and Mn 2 O 3

The intense, highly localized electronic excitation resulting from swift heavy ion irradiation induces phase transformations in many materials, including the lanthanide sesquioxides (Ln 2 O 3 ). To explore the effects of chemical composition on radiation-induced transformations, the structural responses of several related sesquioxides to swift heavy ion irradiation were compared. Polycrystalline Nd 2 O 3 , Eu 2 O 3 , Yb 2 O 3 , and Mn 2 O 3 were irradiated by 946 MeV Au ions to a range of ion fluences up to 2 × 10 13 cm -2 , and structural modifications were characterized using beamline-based in situ x-ray diffraction (XRD) and Rietveld refinement. Amorphization was induced in Nd 2 O 3 , Eu 2 O 3 , and Mn 2 O 3 , with the extent of the induced transformation following a clear dependence on cation ionic radius. Nd 2 O 3 and Eu 2 O 3 , having the largest cations, rapidly amorphized, whereas Mn 2 O 3 , having the smallest cation, experienced only a slight loss of crystallinity at the highest fluences studied. The radiation response was different for Yb 2 O 3 , which underwent a sluggish transformation to a nonequilibrium X-type phase. Furthermore, the crystalline-to-amorphous transformations proceeded by direct-impact mechanisms, while the C-to-X transformation proceeded by a multi-impact mechanism.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Electronic and catalytic engineering in two-dimensional vdW metal–organic frameworks through alloying

Bimetallic metal-organic framework (MOF s ) alloys, in which heterogeneous metal clusters are incorporated into their backbone, are capable of highly selective separations and catalysis. Due to limitations in our fundamental understanding of their alloying, however, established methods result in phase-separated or amorphous two-dimensional (2D) MOF s or lack precise control over alloy ratios. Here, our results demonstrate 2D MOF alloys where metal cation ratios (M 1 and M 2 ) in M 1 xM 2 1-x BDC (M 1 or M 2 = Zn, Cu, Ni, Co, Fe, Mn) can be engineered on demand by controlling the metal salt dissociation constants. Resulting MOF alloys exhibit a highly 2D nature with excellent crystallinity and minute control over metal cation ratios. Overall, our experimental and theoretical results show that their electronic bandgaps and photoexcited carrier lifetimes can be engineered by metal cation alloying. Interestingly, 2D alloyed MOF s enable high-efficiency photo-catalytic water reduction performance in Co/Ni MOF alloys owing to the spatially separated metal clusters in 2D MOF alloys.

2D materials↗
DOE OSTI2023

Formation of the C 4 H n + ( n = 2–5) ions upon ionization of acetylene clusters in helium droplets

Infrared (IR) spectroscopy using ultracold helium nanodroplet matrices has proven to be a powerful method to interrogate encapsulated ions, molecules, and clusters. Due to the helium droplets’ high ionization potential, optical transparency, and ability to pick up dopant molecules, the droplets offer a unique modality to probe transient chemical species produced via photo- or electron impact ionization. Here, in this work, helium droplets were doped with acetylene molecules and ionized via electron impact. Ion-molecule reactions within the droplet volume yield larger carbo-cations that were studied via IR laser spectroscopy. This work is focused on cations containing four carbon atoms. The spectra of C 4 H 2 + , C 4 H 3 + , and C 4 H 5 + are dominated by diacetylene, vinylacetylene, and methylcyclopropene cations, respectively, which are the lowest energy isomers. On the other hand, the spectrum of C 4 H 4 + ions hints at the presence of several co-existing isomers, the identity of which remains to be elucidated.

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

The photoionization of methoxymethanol: Fingerprinting a reactive C 2 oxygenate in a complex reactive mixture

Methoxymethanol (CH 3 OCH 2 OH) is a reactive C 2 ether-alcohol that is formed by coupling events in both heterogeneous and homogeneous systems. It is found in complex reactive environments—for example those associated with catalytic reactors, combustion systems, and liquid-phase mixtures of oxygenates. Using tunable synchrotron-generated vacuum-ultraviolet photons between 10.0 and 11.5 eV, we report on the photoionization spectroscopy of methoxymethanol. We determine that the lowest-energy photoionization process is the dissociative ionization of methoxymethanol via H-atom loss to produce [C 2 H 5 O 2 ] + , a fragment cation with a mass-to-charge ratio (m/z) = 61.029. Here, we measure the appearance energy of this fragment ion to be 10.24 ± 0.05 eV. The parent cation is not detected in the energy range examined. To elucidate the origin of the m/z = 61.029 (C 2 H 5 O 2 ) fragment, we used automated electronic structure calculations to identify key stationary points on the cation potential energy surface and compute conformer-specific microcanonical rate coefficients for the important unimolecular processes. The calculated H-atom dissociation pathway results in a [C 2 H 5 O 2 ] + fragment appearance at 10.21 eV, in excellent agreement with experimental results.

Hansen, Niko A.↗