30 Search Results

The stability and distributions of small water clusters generated in a supersonic beam expansion are interrogated by tunable vacuum ultraviolet (VUV) radiation generated at a synchrotron. Time-of-flight mass spectrometry reveals enhanced population of various protonated water clusters (H⁺(H₂O)_$$n$$) based upon ionization energy and photoionization distance from source, suggesting there are "magic" numbers below the traditional $$n$$ = 21 that predominates in the literature. These intensity distributions suggest that VUV threshold photoionization (11.0-11.5 eV) of neutral water clusters close to the nozzle exit leads to a different nonequilibrium state compared to a skimmed molecular beam. This results in the appearance ofmore » a new magic number at 14. Metadynamics conformer searches coupled with modern density functional calculations are used to identify the global minimum energy structures of protonated water clusters between $$n$$ = 2 and 21, as well as the manifold of low-lying metastable minima. New lowest energy structures are reported for the cases of $$n$$ = 5, 6, 11, 12, 16, and 18, and special stability is identified by several measures. These theoretical results are in agreement with the experiments performed in this work in that $$n$$ = 14 is shown to exhibit additional stability, based on the computed second-order stabilization energy relative to most cluster sizes, though not to the extent of the well-known $$n$$ = 21 cluster. Other cluster sizes that show some additional energetic stability are $$n$$ = 7, 9, 12, 17, and 19. To gain insight into the balance between ion-water and water-water interactions as a function of the cluster size, an analysis of the effective two-body interactions (which sum exactly to the total interaction energy) was performed. In conclusion, this analysis reveals a crossover as a function of cluster size between a water-hydronium-dominated regime for small clusters and a water-water-dominated regime for larger clusters around $$n$$ = 17.« less

Here we used aerosol mass spectrometry coupled with tunable synchrotron photoionization to measure radical and closed-shell species associated with particle formation in premixed flames and during pyrolysis of butane, ethylene, and methane. We analyzed photoionization (PI) spectra for the C₇H₇ radical to identify the isomers present during particle formation. For the combustion and pyrolysis of all three fuels, the PI spectra can be fit reasonably well with contributions from four radical isomers: benzyl, tropyl, vinylcyclopentadienyl, and o-tolyl. Although there are significant experimental uncertainties in the isomeric speciation of C7H₇, the results clearly demonstrate that the isomeric composition of C₇H₇ stronglymore » depends on the combustion or pyrolysis conditions and the fuel or precursors. Fits to the PI spectra using reference curves for these isomers suggest that all of these isomers may contribute to m/z 91 in butane and methane flames, but only benzyl and vinylcyclopentadienyl contribute to the C₇H₇ isomer signal in the ethylene flame. Only tropyl and benzyl appear to play a role during pyrolytic particle formation from ethylene, and only tropyl, vinylcyclopentadienyl, and o-tolyl appear to participate during particle formation from butane pyrolysis. There also seems to be a contribution from an isomer with an ionization energy below 7.5 eV for the flames but not for the pyrolysis conditions. Kinetic models with updated and new reactions and rate coefficients for the C₇H₇ reaction network predict benzyl, tropyl, vinylcyclopentadienyl, and o-tolyl to be the primary C₇H₇ isomers and predict negligible contributions from other C₇H₇ isomers. These updated models provide better agreement with the measurements than the original versions of the models but, nonetheless, underpredict the relative concentrations of tropyl, vinylcyclopentadienyl, and o-tolyl in both flames and pyrolysis and overpredict benzyl in pyrolysis. Our results suggest that there are additional important formation pathways for the vinylcyclopentadienyl, tropyl, and o-tolyl radicals and/or loss pathways for the benzyl radical that are currently unaccounted for in the present models.« less

A new generation of electronic cigarettes is exacerbating the youth vaping epidemic by incorporating additives that increase the acidity of generated aerosols, which facilitate uptake of high nicotine levels. We need to better understand the chemical speciation of vaping aerosols to assess the impact of acidification. Here we used X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to probe the acid-base equilibria of nicotine in hydrated vaping aerosols. Here we show that, unlike the behavior observed in bulk water, nicotine in the core of aqueous particles was partially protonated when the pH of the nebulized solutionmore » was 10.4, with a fraction of free-base nicotine (α_FB) of 0.34. Nicotine was further protonated by acidification with equimolar addition of benzoic acid (α_FB = 0.17 at pH 6.2). By contrast, the degree of nicotine protonation at the particle surface was significantly lower, with 0.72 < α_FB < 0.80 in the same pH range. The presence of propylene glycol and glycerol completely eliminated protonation of nicotine at the surface (α_FB = 1) while not affecting significantly its acid-base equilibrium in the particle core. These results provide a better understanding of the role of acidifying additives in vaping aerosols, supporting public health policy interventions.« less

Water-cluster interactions with polycyclic aromatic hydrocarbons (PAHs) are of paramount interest in many chemical and biological processes. Here we report a study of anthracene monomers and dimers with water (up to four)-cluster systems utilizing molecular beam vacuum-UV photoionization mass spectrometry and density functional calculations. Structural loss in photoionization efficiency curves when adding water indicates that various isomers are generated, while theory indicates only a slight shift in energy in photoionization states of different isomers. Calculations reveal that the energetic tendency of water is to remain clustered and not to disperse around the PAH. Theoretically, we observe water confinement exclusively inmore » the case of four water clusters and only when the anthracenes are in a cross configuration due to optimal OH∙∙∙π interactions, indicating dependence on the size and structure of the PAH. Furthermore theory sheds light on the structural changes that occur in water upon ionization of anthracene, due to the optimal interactions of the resulting hole and water hydrogen atoms.« less

Aqueous aerosols are important in atmospheric chemistry, drug delivery, and human health. X-ray photoelectron spectroscopy (XPS), a surface-sensitive technique and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy which informs on the bulk, is deployed to study the solvation of ammonium nitrate (NH₄NO₃). Aerosolised solutions of NH₄NO₃ were introduced into a photoelectron spectrometer via an aerodynamic lens, and interrogated with soft X-ray photons, the resulting electrons were imaged via velocity map imaging. Density functional theory calculations were performed to compare with the measured binding energies of NH₄⁺ and NO₃^- solvated in water. The results reveal that the nitrate anion has amore » slight propensity for the surface, while both ammonium and nitrate ions are present in equal measure in the bulk.« less

To develop chemical kinetics models for the combustion of ionic liquid-based monopropellants, identification of the elementary steps in the thermal and catalytic decomposition of components such as 2-hydroxyethylhydrazinium nitrate (HEHN) is needed but is currently not well understood. The first decomposition step in protic ionic liquids such as HEHN is typically the proton transfer from the cation to the anion, resulting in the formation of 2-hydroxyethylhydrazine (HEH) and HNO₃. In the first part of this investigation, the high-temperature thermal decomposition of HEH is probed with flash pyrolysis (<1400 K) and vacuum ultraviolet (10.45 eV) photoionization time-of-flight mass spectrometry (VUV-PI-TOFMS). Next,more » the investigation into the thermal and catalytic decomposition of HEHN includes two mass spectrometric techniques: (1) tunable VUV-PI-TOFMS (7.4-15 eV) and (2) ambient ionization mass spectrometry utilizing both plasma and laser ionization techniques whereby HEHN is introduced onto a heated inert or iridium catalytic surface and the products are probed. The products can be identified by their masses, their ionization energies, and their collision-induced fragmentation patterns. Further, formation of product species indicates that catalytic surface recombination is an important reaction process in the decomposition mechanism of HEHN. The products and their possible elementary reaction mechanisms are discussed.« less

Here, the local electronic structure of aqueous histidine, an amino acid important in nature and biology, is revealed by aerosol X-ray photoemission spectroscopy. A detailed picture of the photoionization dynamics emerges by tuning the pH of the aqueous solution from which the aerosols are generated, allowing us to report the X-ray photoelectron spectroscopy (XPS) of histidine. Assignment of the experimental photoelectron spectra of the C1s and N1s levels allows the determination of the protonation state of histidine in these aqueous aerosols and is confirmed by density functional calculations. XPS spectra show that at pH = 1, both imidazole and aminemore » group nitrogens are protonated, at pH = 7, the amine group nitrogen is protonated and the carboxyl group carbon is deprotonated resulting in a zwitterionic structure, and at pH = 13, only the carboxyl group remains deprotonated. Comparison of these results with previous experimental and theoretical results suggests that X-ray spectroscopy on aqueous aerosols can provide a convenient and simple way of probing their electronic structure in aqueous solutions.« less

Air-liquid interfacial processing of volatile organic compound photooxidation has been suggested as an important source of secondary organic aerosols. However, owing to the lack of techniques for studying the air-liquid interface, the detailed interfacial mechanism remains speculative. To obviate this, we enabled in situ synchrotron-based vacuum ultraviolet single photon ionization mass spectrometry using the system for analysis at the liquid-vacuum interface microreactor to study glyoxal photooxidation at the air-liquid interface. Determination of reaction intermediates and new oxidation products, including polymers and oligomers, by mass spectral analysis and appearance energy measurements has been reported for the first time. Furthermore, an expandedmore » reaction mechanism of photooxidation and free radical induced reactions as a source of aqueous secondary organic aerosol formation is proposed. Here, single photon ionization can provide new insights into interfacial chemistry.« less

A study of the formation of microstructures in the reaction of oleic acid with arginine elucidates dynamical self-assembly processes at the molecular level. Terahertz spectroscopy combined with density functional calculations reveals the initial hydrogen-bonding motifs in the assembly process, leading to the formation of micelles and vesicles. Small-angle X-ray scattering measurements allow for kinetic analysis of the growth processes of these nanostructures, revealing a prenucleation pathway of vesicles and micelles which lead to spongelike structures. This final stage of the assembly into spongelike aggregates is investigated with optical microscopy. The formed structures only occur at pH > 8 and aremore » resistant to extreme acidic and basic conditions. Here, a mechanistic pathway to the formation of the spongelike aggregates is described.« less

Corannulene can be formed through molecular mass growth processes in circumstellar envelopes.