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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Low 13 C- 13 C abundances in abiotic ethane

Distinguishing biotic compounds from abiotic ones is important in resource geology, biogeochemistry, and the search for life in the universe. Stable isotopes have traditionally been used to discriminate the origins of organic materials, with particular focus on hydrocarbons. However, despite extensive efforts, unequivocal distinction of abiotic hydrocarbons remains challenging. Recent development of clumped-isotope analysis provides more robust information because it is independent of the stable isotopic composition of the starting material. Here, we report data from a 13 C- 13 C clumped-isotope analysis of ethane and demonstrate that the abiotically-synthesized ethane shows distinctively low 13 C- 13 C abundances compared to thermogenic ethane. A collision frequency model predicts the observed low 13 C- 13 C abundances (anti-clumping) in ethane produced from methyl radical recombination. In contrast, thermogenic ethane presumably exhibits near stochastic 13 C- 13 C distribution inherited from the biological precursor, which undergoes C-C bond cleavage/recombination during metabolism. Further, we find an exceptionally high 13 C- 13 C signature in ethane remaining after microbial oxidation. In summary, the approach distinguishes between thermogenic, microbially altered, and abiotic hydrocarbons. The 13 C- 13 C signature can provide an important step forward for discrimination of the origin of organic molecules on Earth and in extra-terrestrial environments.

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

Directed Gas-Phase Formation of the 1-Cyanovinyl Radical (H 2 CCCN, X 2 A′) in the Interstellar Medium

The formation pathways to nitrogen-containing molecules and radicals are crucial to the understanding of the carbon–nitrogen chemistry in interstellar and atmospheric environments. While over 65 nitrogen-containing neutral species have been observed in deep space to date, their formation mechanisms─in particular, those of radical species─remain largely speculative. The crossed molecular beam technique in conjunction with electronic structure and statistical calculations was utilized to offer a detailed overview of the fundamental pathways in the gas-phase bimolecular reaction of ground-state atomic carbon (C, 3 P) with acetonitrile-d 3 (CD 3 CN, X 1 A 1 ) under single-collision conditions leading to the formation of the 1-cyanovinyl radical (D 2 CCCN, X 2 A′) coupled with deuterium atom loss. Here, the indirect reaction was initiated by barrierless carbon-atom addition, with the most probable route involving carbon addition across the carbon–nitrogen nitrile triple bond of acetonitrile, forming a three-membered ring intermediate followed by ring-opening and unimolecular decomposition via atomic deuterium loss from the C3 carbon atom. The reaction was overall exoergic, and intermediates and transition states lie lower in energy than the separated reactants, unlocking the reaction of carbon with acetonitrile in low-temperature environments such as cold molecular clouds, e.g., Taurus Molecular Cloud (TMC-1), and planetary atmospheres, e.g., Saturn’s moon Titan. In these environments, the 1-cyanovinyl radical may act as a building block for cyano-substituted polycyclic aromatic hydrocarbons and N-heterocycles, thus furthering our understanding of the complex carbon–nitrogen chemistry in deep space.

Chemical reactions↗
DOE OSTI2020

Solving complex eigenvalue problems on a quantum annealer with applications to quantum scattering resonances

Quantum computing is a new and rapidly evolving paradigm for solving chemistry problems. In previous work, we developed the Quantum Annealer Eigensolver (QAE) and applied it to the calculation of the vibrational spectrum of a molecule on the D-Wave quantum annealer. However, the original QAE methodology was applicable to real symmetric matrices only. For many physics and chemistry problems, the diagonalization of complex matrices is required. For example, the calculation of quantum scattering resonances can be formulated as a complex eigenvalue problem where the real part of the eigenvalue is the resonance energy and the imaginary part is proportional to the resonance width. In the present work, we generalize the QAE to treat complex matrices: first complex Hermitian matrices and then complex symmetric matrices. These generalizations are then used to compute a quantum scattering resonance state in a 1D model potential for O + O collisions. These calculations are performed using both a software (classical) annealer and hardware annealer (the D-Wave 2000Q). The results of the complex QAE are also benchmarked against a standard linear algebra library (LAPACK). Furthermore, this work presents the first numerical solution of a complex eigenvalue problem of any kind on a quantum annealer, and it is the first treatment of a quantum scattering resonance on any quantum device.

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

Functionalization of Electrodes with Tunable [EMIM] x [Cl] x +1 – Ionic Liquid Clusters for Electrochemical Separations

Functionalization of electrodes with clusters of hydrophobic molecules may improve the energy efficiency and selectivity of electrochemical separations by modulating the desolvation process occurring at the interface. Ionic liquids (IL), which have a broad range of compositions and properties, are potential candidates for controlling the transport, desolvation, and adsorption of target ions at electrochemical interfaces. We report a joint experimental and theoretical investigation of the structure, stability, and selective adsorption properties of the IL clusters 1-ethyl-3-methylimidazolium chloride [EMIM] x [Cl] x+1 - (x = 1 – 10) and demonstrate their ability to adsorb and separate ions from solution. The structure and stability of the IL clusters are determined experimentally using high-mass-resolution electrospray ionization mass spectrometry, collision-induced dissociation, and negative ion photoelectron spectroscopy. Global optimization theory and ab initio molecular dynamics simulations provide molecular-level insight into the bonding and structural fluxionality of these species. Ion soft landing is used to selectively functionalize the surface of highly oriented pyrolytic graphite (HOPG) working electrodes with [EMIM] 1 [Cl] 2 - , [EMIM] 3 [Cl] 4 - , and [EMIM] 5 [Cl] 6 - clusters. Kelvin probe microscopy provides insight into the relative stability of the clusters on HOPG and their effect on the work function of IL-functionalized electrodes. Cyclic voltammetry measurements reveal irreversible adsorption of Fe(CN) 6 4-/3- anions during redox cycling, while electrochemical impedance spectroscopy indicates a substantial decrease in the electron transfer resistance of the IL-functionalized electrodes due to adsorption of Fe(CN) 6 4-/3- . Overall, our findings demonstrate that IL clusters with different size and stoichiometry may be used to increase the efficiency of electrochemical separations, opening new horizons in selective electrode functionalization.

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

Gas-Phase Study of the Elementary Reaction of the D1-Ethynyl Radical (C 2 D; X 2 Σ + ) with Propylene (C 3 H 6 ; X 1 A') under Single-Collision Conditions

The bimolecular gas-phase reactions of the D1-ethynyl radical (C 2 D; X 2 Σ + ) with propylene (C 3 H 6 ; X 1 A’) and partially substituted D3-3,3,3-propylene (C 2 H 3 CD 3 ; X 1 A’) were studied under single collision conditions utilizing the crossed molecular beams technique. Combining our laboratory data with electronic structure and statistical calculations, the D1-ethynyl radical is found to add without barrier to the C1 and C2 carbons of the propylene reactant, resulting in doublet C 5 H 6 D intermediate(s) with lifetime(s) longer than their rotational period(s). These intermediates undergo isomerization and unimolecular decomposition via atomic hydrogen loss through tight exit transition states forming predominantly cis/trans-3-penten-1-yne ((HCC)CH=CH(CH 3 )) and to a minor amount 3-methyl-3-buten-1-yne ((HCC)C(CH 3 )=CH 2 ) via overall exoergic reactions. Although the title reaction does not lead to the cyclopentadiene molecule (c-C 5 H 6 , X 1 A 1 ), high temperature environments can convert the identified acyclic C 5 H 6 isomers through hydrogen atom assisted isomerization to cyclopentadiene (c-C 5 H 6 , X 1 A 1 ). Since both the ethynyl radical and propylene reactants have been observed in cold interstellar environments such as TMC-1 and the reaction is exoergic and all barriers lie below the energy of the separated reactants, the these C 5 H 6 product isomers are predicted to form in those low temperature regions.

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

Molecular dynamics simulations of reflection and sputtering behavior of boron under deuterium ion irradiation

Boronization is a commonly used method of wall conditioning in fusion reactors. The application of boron films to the plasma-facing materials results in enhanced plasma performance due to the reduction of intrinsic impurities. This is primarily driven by a reduction in oxygen content that is chemically trapped in the boron film. The reactive nature of these boron films also raises questions concerning interactions with hydrogen isotopes. In this work, boron-deuterium interactions were studied using molecular dynamics (MD). Reactive force field potentials were used to model the chemical interactions between B and D. An amorphous boron substrate was irradiated by D atoms at varying incident energies, 10 eV < E i < 150 eV and angles, 0° < α < 85°. The reflection probability was calculated and compared to results from the commonly-used binary collision approximation (BCA) method. This comparison found that the BCA underestimated the reflection probability at E i < 35 eV and α > 45 ∘ . The source of this discrepancy was found to be the surface binding energy model. The BCA calculation with an isotropic surface binding energy model was more closely aligned to the MD result. This, in combination with a correction function based on the MD results allows for corrections to the reflection probability of deuterium impinging on boron surfaces. The sputtering of the substrate material was also studied. While this study did not contain sufficient events to quantitatively describe the sputtering behavior, some qualitative results emerged: namely, chemical sputtering of B and D-containing molecules (BD, BD 2 , BD 3 ) at low ( < 20 eV) incident deuterium energies. This result suggests that chemical sputtering could be a significant factor in limiting boron coating lifetime when exposed to lower ion energies, such as those in detached plasmas. The results show that chemical interactions should be taken into account when modeling the interactions between D ions and B surfaces.

Boron↗
DOE OSTI2021

Linear polarization fractions of Fulcher- α fluorescence in electron collisions with H 2

We apply the molecular convergent close-coupling method to the calculation of linear polarization fractions for Fulcher-band fluorescence following electron-impact excitation of the H 2 d 3 Π u state. Furthermore, the results exhibit the opposite threshold behavior compared to the only previous calculations, but are in agreement with the most recent measurements for the Q(1), R(1), and Q(3) transitions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Effect of interfacial vibrational coupling on surface wettability and water transport

Here, we report that the atomic-scale vibrational coupling at the solid-fluid interface can substantially alter the interfacial properties such as wettability and fluid slip. The wettability of water droplets on substrates subjected to various vibrational frequencies is studied using molecular dynamics simulation. The contact angle increases (i.e., becomes more hydrophobic) when the oscillation frequency of the substrate matches the intermolecular bending frequency of liquid water. We investigate the underlying mechanism by examining the dynamics of water molecules at the interface and find that the temporal contact between the solid and fluid is shorter when the frequencies match, resulting in weak solid-fluid adsorption. We further report that the vibrational match at the interface reduces wall-fluid friction and enhances water transport through the nanopore. Our findings demonstrate the importance of the atomic-scale vibrational coupling at the solid-fluid interface on the physicochemical behavior of nanodevices and biological nanochannels.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Prospects for detecting UF6 hydrolysis intermediates by mass spectrometry, resonance Raman, and NQR spectroscopy

Simulations are performed to consider several spectrometric and spectroscopic candidates for elucidating the mechanism of the hydrolysis of uranium hexafluoride (UF6). This study is among the first to benchmark the def-mTZVP basis sets for actinide-containing molecules, and it is shown to be a suitable basis set for surveying geometrical structures and vibrational spectra when used in conjunction with density functional theory. An experiment is proposed coupling mass spectrometric ion selection with vibrational spectroscopy, and supporting infrared and Raman spectral simulations demonstrate that ionization blue-shifts bands and can change their qualitative features. Ultraviolet resonance Raman is shown to have good prospects for discriminating U–O–U bridged intermediates, evidence for which was observed recently [L. E. McNamara et al., J. Phys. Chem. A 130, 775–786 (2026)]. As a more speculative approach, we also consider the prospect of addressing 233U or 235U nuclei by quadrupole resonance (NQR) spectroscopy for assigning early stage intermediate complexes. In doing so, we provide a first order-of-magnitude estimate for the collision-induced NQR signal for the UF6 dimer, which is of interest for the interpretation of a fast decoherence time observed in liquid-phase nuclear magnetic resonance. Having provided critical insights into the formation and stability of UF6 hydrolysis intermediates in previous studies, this computational spectroscopy survey is expected to help guide and expedite future laboratory campaigns.

Lutz, Jesse J. [Center for Computing Research, San↗
DOE OSTI2026

Dynamics of iodine geminate recombination in supercritical xenon solvent: Caging effect

Understanding the dynamics of chemical reactions in solutions is vital, as their rates and kinetics are significantly affected by the solvent environment. Supercritical solvents offer extensive applications in chemical reactions by enabling the manipulation of the solution environment. Here, in this study, we investigate the geminate recombination of iodine in a supercritical xenon solvent by using ReaxFF-based molecular dynamics simulations. Our findings reveal that the highest iodine recombination rate occurs near supercritical conditions, while lower-pressure conditions lead to reduced collision rates and unstable recombination, and higher-pressure conditions hinder iodine diffusion, resulting in a lower recombination rate. Our analysis shows that the xenon local density at the time of recombination is at least 2.5 times higher than the global density, confirming the presence of xenon clusters surrounding the Iodine atoms. This observation is further supported by coordination number analysis, which confirms an elevated xenon local density during recombination. In addition, the correlation between the total energy of xenon atoms within a cluster and recombined iodine atoms underscores the kinetic energy transfer process, validating the occurrence of geminate recombination. The excess kinetic energy from the recombining iodine atoms is transferred to the surrounding xenon atoms. Our examination of geminate recombination demonstrates that iodine atoms confined within xenon clusters—whether through manual insertion of atoms or the fast dissociation of an iodine molecule within xenon clusters—are more likely to recombine as primary geminate recombination. However, extending the iodine molecule dissociation time allows iodine atoms to diffuse out of the cluster, and the recombination to shift toward secondary geminate recombination.

Cage effect↗
DOE OSTI2023

Automated identification and calculation of prompt effects in kinetic mechanisms using statistical models

The kinetics of prompt dissociation involves rovibrationally excited species (generally formed by exothermic reactions) which may dissociate or isomerize prior to thermalization via collisions with the bath gas. Treating such rovibrationally excited species (so-called "hot" species) with standard kinetic phenomenology may result in incorrect macroscopic representation of their reactivity. Here this work presents the first fully automated methodology for the calculation of prompt effects of a chosen species in a kinetic mechanism, including (i) reaction selection; (ii) theoretical calculation of rate constants and prompt branching fractions; and (iii) final rate constant fitting. The energy partition between hot fragments is estimated using a variety of statistical models, including a new physically sound microcanonical statistical model based on the rovibrational density of states of the fragments. The methodology is validated against literature data for the prompt dissociations of HCO and C 3 H 7 radicals. The microcanonical statistical model is in better agreement with trajectory simulations for larger species and is thus applicable for practical systems that typically involve large molecules, for which direct dynamics calculations are impractical. The automated workflow is applied to the evaluation of the effects of prompt dissociation for two isomeric radicals C 4 H 7 1-3 (1-methylallyl) and C 4 H 7 1-4 (3-buten-1-yl). Twelve H-atom abstraction reactions are selected and the corresponding rate constants are computed with first principles theory. The microcanonical statistical model predicts that prompt dissociations of C 4 H 7 1-3 and C 4 H 7 1-4 are already significant at 1000K, resulting in differences of up to an order of magnitude at 2000K with respect to the phenomenological thermal rate constants. To illustrate the effects of prompt dissociation on simulations of experimental data, the calculated prompt rate constants are implemented in both CRECK and C3MechV3.3 kinetic mechanisms. Simulations of experimental flame data illustrate the noticeable impact of prompt dissociation kinetics on the high-temperature combustion reactivity of C 4 H 8 -1 and C 4 H 8 -2.

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

Oxygenated Molecules measured with a Nitrate Chemical Ionization Mass Spectrometer

These files contain selected oxygenated compounds detected by chemical ionization mass spectrometry with nitrate reagent ion. Detected compounds were grouped by volatility and the time series of the most intense ions in each volatility class are provided here. Volatility (C*) in units of μg m^-3 was calculated using log_10(C*)=(n_ref -n_C)*b_C - (n_O - 3*n_N)*b_O - 2*(((n_O - 3n_N)*n_C) / (n_C + n_O - 3*n_N))*b_CO - n_N* b_N where n_ref = 25, b_c = 0.475m b_O = 0.2, b_N = -0.5, b_CO = 0.9, n_C is the number of carbon atoms in the ion formula, n_O is the number of oxygen atoms in the ion formula, and n_N is the number of nitrogen atoms in the ion formula. Volatility was calculated for each formula (with the nitrate anion excluded) and compounds were assigned into extremely low volatility (ELVOCs, C* < 10^−4.5 μg m^-3), low volatility (LVOCs, 10^−4.5 μg m^-3 ≤ C* < 10^−0.5 μg m^-3), or semi-volatile (SVOCs, 10^−0.5 μg m^-3 ≤ C* < 10^2.5 μg m^-3) bins. All ions were assumed to be detected with a collision-limited sensitivity and thus represent lower bound values. Values are reported as parts per trillion by volume mixing ratio.

Extremely low-volatility organic compounds↗
DOE OSTI2022

On the use of stereodynamical effects to control cold chemical reactions: The H + D 2 ↔ D + HD case study

Here, quantum calculations are reported for the stereodynamic control of the H + D 2 ↔ D + HD chemical reaction in the energy range of 1–50 K. Stereodynamic control is achieved by a formalism similar to that reported by Perreault et al. [Nat. Chem. 10, 561 (2018)] in recent experimental works in which the alignment of the molecular bond axis relative to the incident relative velocity is controlled by selective preparations of the molecule in a specific or superposition of magnetic projection quantum numbers of the initial molecular rotational level. The approach presented here generalizes the experimental scheme of Perreault et al. and offers additional degree of control through various experimental preparations of the molecular alignment angle. Illustrative results presented for the H + D 2 and D + HD reactions show significant control with the possibility of turning the reaction completely on or off with the appropriate stereodynamic preparation of the molecular state. Various scenarios for maximizing and minimizing the reaction outcomes are identified with the selective preparation of molecular rotational states.

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

Solid-to-plasma transition of polystyrene induced by a nanosecond laser pulse within the context of inertial confinement fusion

Laser Direct Drive (LDD) Inertial Confinement Fusion (ICF) involves irradiating a spherical target of thermonuclear fuel coated with an ablator, usually made of polystyrene. Laser energy absorption near the target surface leads to matter ablation, hydrodynamic shocks, and ultimately capsule implosion. The conservation of spherical symmetry is crucial for implosion efficiency, yet spatial modulations in laser intensity can induce nonuniformities, causing the laser imprint phenomenon. Understanding laser imprint, especially considering the initial solid state, is essential for advancing LDD ICF. A first microscopic model of solid-to-plasma transition was built in 2019, accounting for laser absorption in the solid state with a band structure based ionization model. This model has been improved to include chemical fragmentation and a more accurate description of electron collision frequency in various matter states. The latest development involves assessing the model reliability by comparing theoretical predictions with experimental observations. Despite the success of this approach, questions remain, leading to further investigations and observations under different irradiation conditions. This work presents an experiment with a nanosecond pulse, taking into account hydrodynamic effects, and measures transmission dynamics over the entire laser beam area to observe two-dimensional effects. As a result, the objective is to adapt the theoretical model, couple it with a hydrodynamic code, and observe additional effects related to the initial solid state.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Assessing the Impact of Measurement Precision on Metabolite Identification Probability in Multidimensional Mass Spectrometry-Based, Reference-Free Metabolomics

Identification of compounds with minimal ambiguity remains a central challenge in mass spectrometry-based metabolomics. Conventional compound identification relies on comparing analytical signatures (e.g., mass-to-charge ratio, collision cross section, tandem mass spectra) against reference data obtained from measurements of authentic chemical standards. The breadth of annotatable compounds using this approach is necessarily limited by availability of authentic standards, analytical throughput, and resolving power of the separations that underly the measurements. The maturation of computational methods, both theory-driven and artificial intelligence/machine learning-based, for prediction of various molecular properties relevant to multidimensional mass spectrometry measurements has opened the door to a new “reference-free” paradigm of compound annotation. Through augmenting existing reference data for molecular properties with computational predictions, the universe of identifiable chemical species can be expanded significantly beyond its current limits. An unexplored aspect of this novel approach is understanding how to gauge confidence in resulting annotations, especially as the compound search space is expanded. Intuitively, the confidence of a compound annotation is related to the inherent discriminatory power of the molecular properties used for identification, as well as the precision with which the properties are measured or predicted. In this work, we characterize this relationship between measurement precision and identification probability in a systematic and quantitative fashion for a defined region of chemical space that includes organic small molecule metabolites. Importantly, this work establishes a framework for conducting metabolite identification probability analysis that enables others to quantify this relationship for their own compounds and properties of interest.

Metabolite Identification↗
DOE OSTI2021

Preliminary Evidence of Gas-Phase Water Splitting on Holmium Nitrogen Oxide Clusters

Preliminary Evidence of Gas-Phase Water Splitting on Holmium Nitrogen Oxide Clusters Christopher A. Zarzana1, Makayla R. Baxter , Introduction: Molecular hydrogen is a potential energy carrier that could be used to help implement a clean energy economy if it is generated from splitting of water. Improvements in the efficiencies of water-splitting electrolyzers relies on development of novel materials with enhanced performance. However, research in this area is slowed due to underdeveloped understanding of the mechanisms of device performance due to challenges interrogating the fundamental chemical reactions at play in bulk materials. Studies of the intrinsic reactivity of clusters that are representative of the reactive sites of these materials can increase understanding of the fundamental reaction mechanisms involved in hydrogen production, allowing for more efficient development of new water-splitting materials. Methods: Holmium tetranitrato ([Ho(NO3)4]-) clusters were generated in gas-phase using the electrospray ionization source of a Bruker (Billerica, MA, USA) micrOTOF-Q II quadrupole time-of-flight mass spectrometer. Spray solutions consisted of aqueous holmium (Ho) nitrate solutions (at nominally 3 mM) diluted to 30 µM in acetonitrile. The holmium (Ho) tetranitrato clusters were isolated using the quadrupole and were subsequently activated and allowed to react with background water in the collision cell. High resolution, high mass accuracy spectra were recorded using the time-of-flight. Mass accuracy was ensured using external calibration with Agilent (Santa Clara, CA, USA) ESI-L Low Concentration tuning mix. Preliminary data: Collisional activation of the holmium tetranitrato complexes ([Ln(NO3)4]-) resulted in an expected series of ions resulting from the loss of ·NO and ·NO2. This included an ion at m/z = 382.885 assigned as [HoO2(NO3)3]- (theoretical m/z=382.884, error=-1.2 ppm), resulting from loss of ·NO, and an ion at m/z=366.890 assigned as [HoO(NO3)3]- (theorical m/z=366.889, error=-1.8 ppm), resulting from loss of ·NO2. Additional ions were detected that would result from more complicated losses from [Ho(NO3)4]-, including ions at m/z=320.898 assigned as [HoO2(NO3)2]- (theoretical m/z=320.896, error=-4.9 ppm), at m/z=304.904 assigned as [HoO(NO3)2]- (theoretical m/z=304.901, error=-8.1 ppm, very low signal), and at m/z=288.908 assigned as [Ho(NO3)2]- (theoretical m/z=288.907, error=-3.4 ppm). This ion series would arise from loss of some combination of ·NO, ·NO2, and ·NO3, although it is not known whether these losses occur sequentially (e.g. loss of ·NO and ·NO3 to yield [HoO2(NO3)2]-) or as a single species (e.g. direct loss of N2O4). These ions were accompanied by a complementary series representing addition of a single water molecule. This included an ion at m/z=338.908 assigned as [HoO2(NO3)2H2O]- (theoretical m/z=338.907, error=-4.1 ppm), an ion at m/z=322.912 assigned as [HoO(NO3)2H2O]- (theoretical m/z=322.912, error=1.2 ppm), and an ion at m/z=306.918 assigned as [Ho(NO3)2H2O]-, (theoretical m/z=306.918, error=-3.7 ppm). An additional hydrated ion was observed at m/z=276.921 assigned as [HoO2(NO3) H2O]- (theoretical m/z=276.919, error=-7.3 ppm), although corresponding dehydrated ion was not observed. An additional ion was observed at m/z=367.898 that has been assigned as [Ho(NO3)3OH]- (theoretical m/z=367.897, error=-2.5 ppm). It is hypothesized that this ion arises from addition of water to [Ho(NO3)3]- followed by elimination of a hydrogen radical. Neither [Ho(NO3)3]- nor [Ho(NO3)3H2O]- were detected, suggesting that, if the hypothesis is correct, addition of water to [Ho(NO3)3]- and its subsequent splitting is rapid. Elimination of HNO3 from [Ho(NO3)4H2O]- could also yield [Ho(NO3)3OH]-; however, no [Ho(NO3)4H2O]- ions were observed. Novelty: Potential evidence of water splitting on gas-phase lanthanide clusters offers a way to study the intrinsic reactivity of hydrogen-generation materials.

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

Ambient Ion Trapping and Separations for High Throughput Structurally Selective Material Deposition

While ion mobility coupled to mass spectrometry (IMS/MS) has been increasingly adapted to biological analysis, the structural and molecular specificity offered by IMS/MS has untapped potential for creating novel materials (for energy, catalysis, biomolecular switches etc.) with rationally tailored properties by precisely controlling the chemical structure and composition of these materials. While electrochemical and catalytic properties of the bulk material are understood by mass-selective ion-soft-landing, different structures of one molecule can exhibit distinct properties from the bulk. Many biological phenomenon occur at interfaces and are highly structurally specific. IMS/MS offers means to separate molecules in a sample (which is first ionized and released to gas phase from the condensed phase) based on mass and structure. Species thus separated can potentially be deposited onto surfaces with molecular and structural specificity, to perform fundamental investigations for understanding critical interfacial phenomenon. Key performance metrics for IMS/MS analysis are resolution of separations and sensitivity. Recently developed Structures for Lossless Ion Manipulations (SLIM)4 enabled unprecedented resolution in IMS separations. In addition, high sensitivity was enabled in SLIM due to lossless confinement of ions using radio frequency fields. Thus, SLIM enabled extremely long path length separations (up to 0.1 km thus far) providing efficient separation of molecular ions never before achieved (e.g. isotopologues, D&L amino acids). While SLIM has unprecedented analytical separations power/utility, the use of SLIM platform for depositing mobility and mass selected molecular ions has two specific technological challenges: (a) Pulsed nature of IMS separations and their low duty cycle and (b) the need for a low vacuum of ~4 torr for lossless ion confinement. These limitations lead to long deposition times due to loss of ions generated from the sample. Enabling ion confinement at atmospheric pressure will be path-breaking contribution to the fundamental understanding of ion manipulations and separations and will also enable novel science currently precluded due to the inability of the present technologies to confine ions under ambient conditions. Traditionally used radio frequency fields are ineffective in confining ions at high pressures due to ion/neutral collisions. To address these, we propose to (a) develop methods for confining and manipulating ions for lossless IMS separations at atmospheric pressure enabling high sensitivity and throughput and (b) use the high specificity of IMS/MS and high throughput from ambient ion confinement to perform mobility and mass selective ion deposition at atmospheric pressure. Our goal is to enable the study of the fundamental properties of energy/catalysis materials and biomolecules. This project paves the way for high-throughput, mass and structure selective material deposition for highly specific surface creation/functionalization (discussed in Section 2 of the report). Further, the developments reported continue to push the boundaries of this process to ambient conditions (discussed in Section 3 of the report). We conclude with a list of specific intellectual property and publications which have been the outcome of this funded project.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Computational tools and algorithms for ion mobility spectrometry-mass spectrometry

Ion mobility spectrometry-mass spectrometry (IMS-MS or IM-MS) is a powerful analytical technique that combines the gas-phase separation capabilities of IM with the identification and quantification capabilities of MS. IM-MS can differentiate molecules with indistinguishable masses but different structures (e.g., isomers, isobars, molecular classes, and contaminant ions). The importance of this analytical technique is reflected by a staged increase in the number of applications for molecular characterization across a variety of fields, from different MS-based omics (proteomics, metabolomics, lipidomics, etc.) to the structural characterization of glycans, organic matter, proteins, and macromolecular complexes. With the increasing application of IM-MS there is a pressing need for effective and accessible computational tools. This article presents an overview of the most recent free and open-source software tools specifically tailored for the analysis and interpretation of data derived from IM-MS instrumentation. This review enumerates these tools and outlines their main algorithmic approaches, while highlighting representative applications across different fields. Finally, a discussion of current limitations and expectable improvements is presented.

59 BASIC BIOLOGICAL SCIENCES↗