The chemistry of ortho-benzyne (o-C6H4) is of fundamental importance due to its role as an essential molecular building block in molecular-weight growth reactions. Here, we report on an experimental investigation...

Synthetic routes to the 10π Hückel aromatic azulene (C10H8) molecule, the simplest polycyclic aromatic hydrocarbon carrying an adjacent five- and seven-membered ring, have been of fundamental importance due to the role of azulene - a structural isomer of naphthalene - as an essential molecular building block of saddle-shaped carbonaceous nanostructures such as curved nanographenes and nanoribbons. Here, we report on the very first gas phase preparation of azulene by probing the gas-phase reaction between two resonantly stabilized radicals, fulvenallenyl and propargyl , in a molecular beam through isomer-resolved vacuum ultraviolet photoionization mass spectrometry. Augmented by electronic structure calculations, the novel Fulvenallenyl Addition Cyclization Aromatization (FACA) reaction mechanism affords a versatile concept for introducing the azulene moiety into polycyclic aromatic systems thus facilitating an understanding of barrierless molecular mass growth processes of saddle-shaped aromatics and eventually carbonaceous nanoparticles (soot, interstellar grains) in our universe.

Radical-radical reactions contribute to molecular weight growth of polycyclic aromatic hydrocarbons (PAHs), but their role is not well understood. The phenyl (Ph, C6H5) + cyclopentadienyl (C5H5) reaction has not been studied but can serve as a surrogate reaction for many reactions of larger aryl-a radicals with resonance-stabilized ir-radicals. The adducts of these reactions easily lose an H atom to produce a new ir-radical. Through a combination of dilute flash pyrolysis experiments, theory, and simulation, we find that for the title reaction, substantial Ph -C5H4 + H is formed, dominantly by a well-skipping pathway, at conditions around 30 Torr and 1400 K. This radical is thermally stable at moderate temper-atures but decomposes at higher temperatures following ring opening of the 5-member ring. Products corresponding to the loss of H, C2H2, and C3H3 are observed experimentally. Calculation of the C11H9 potential energy surface affirms that these are expected decomposition products and reveals multiple possible pathways. (c) 2022 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

The gas-phase reaction of two resonantly stabilized radicals synthesizes the 10π Hückel aromatic azulene and naphthalene – which can be embedded into saddle-shaped carbonaceous nanostructures exhibiting positive and negative curvatures.

Well-skipping radical-radical reactions can provide a chain-propagating pathway for formation of polycyclic radicals implicated in soot inception. Here we use controlled pyrolysis in a microreactor to isolate and examine the role of well-skipping channels in the phenyl (C 6 H 5 ) + propargyl (C 3 H 3 ) radical-radical reaction at temperatures of 800-1600 K and pressures near 25 Torr. The temperature and concentration dependence of the closed-shell (C 9 H 8 ) and radical (C 9 H 7 ) products are observed using electron-ionization mass spectrometry. The flow in the reactor is simulated using a boundary layer model employing a chemical mechanism based on recent rate coefficient calculations. Comparison between simulation and experiment shows reasonable agreement, within a factor of 3, while suggesting possible improvements to the model. In contrast, eliminating the well-skipping reactions from the chemistry mechanism causes a much larger discrepancy between simulation and experiment in the temperature dependence of the radical concentration, revealing that the well-skipping pathways, especially to form indenyl radical, are significant at temperatures of 1200 K and higher. While most C 9 H 7 forms by well-skipping at 25 Torr, an additional simulation indicates that the wellskipping channels only contribute around 3% of the C 9 H x yield at atmospheric pressure, thus indicating a negligible role of the well-skipping pathways at atmospheric and higher pressures. & COPY; 2022 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

to the product radical forms both triphenylmethane and triphenylmethyl radicals, confirming the propagation of radical–radical chain reactions under the experimental conditions of high temperature (1100–1600 K) and low pressure (ca. 3 kPa). Similar chain reactions may contribute to particle growth in flames, the interstellar medium, and industrial reactors.

Dimethyl ether (DME) oxidation is a model chemical system with a small number of prototypical reaction intermediates that also has practical importance for low-carbon transportation. Although it has been studied experimentally and theoretically, ambiguity remains in the relative importance of competing DME oxidation pathways in the low-temperature autoignition regime. To focus on the primary reactions in DME autoignition, we measured the time-resolved concentration of five intermediates, CH3OCH2OO (ROO), OOCH2OCH2OOH (OOQOOH), HOOCH2OCHO (hydroperoxymethyl formate, HPMF), CH2O, and CH3OCHO (methyl formate, MF), from photolytically initiated experiments. We performed these studies at P = 10 bar and T = 450-575 K, using a high-pressure photolysis reactor coupled to a time-of-flight mass spectrometer with tunable vacuum-ultraviolet synchrotron ionization at the Advanced Light Source. Our measurements reveal that the timescale of ROO decay and product formation is much shorter than predicted by current DME combustion models. The models also strongly underpredict the observed yields of CH2O and MF and do not capture the temperature dependence of OOQOOH and HPMF yields. Adding the ROO + OH → RO + HO2 reaction to the chemical mechanism (with a rate coefficient approximated from similar reactions) improves the prediction of MF. Increasing the rate coefficients of ROO ↔ QOOH and QOOH + O2 ↔ OOQOOH reactions brings the model predictions closer to experimental observations for OOQOOH and HPMF, while increasing the rate coefficient for the QOOH → 2CH2O + OH reaction is needed to improve the predictions of formaldehyde. To aid future quantification of DME oxidation intermediates by photoionization mass spectrometry, we report experimentally determined ionization cross-sections for ROO, OOQOOH, and HPMF.

The discovery of enols in combustion environments and our atmosphere has garnered increasing attention to the many unanswered questions surrounding enol chemistry. The scarcity of experimental data concerning these enols renders combustion and atmospheric models with a lack of constraining parameters, leading to varying computational predictions. Experimental detection is difficult because mass spectrometry, a powerful tool for probing a wide variety of species, cannot distinguish between enols and their thermodynamically favorable ketone isomers. A solution to this ambiguity is to use tunable vacuum ultraviolet (VUV) light from a synchrotron to identify the presence of the enol by its lower ionization energy compared to the isomer. We present a tabletop-scale VUV light source that implements highly cascaded harmonic generation, a new regime of cascaded nonlinear optics, to provide a set of spectral lines spaced by 1.2 eV. We demonstrate that the variety of photon energies available allows us to detect the keto-enol tautomerization of four aldehydes and ketones. By combining this novel VUV light source with an established microreactor, we first revisit the formation of vinyl alcohol from acetaldehyde and confirm that the observed isomerization is indeed unimolecular. Secondly, we observe the thermal tautomerization of acetone to propen-2-ol for the first time. Finally, we observe the thermal tautomerization of cyclohexanone to 1-cyclohexenol and methyl vinyl ketone to 2-hydroxybutadiene, where the results are in good agreement with those reported at a synchrotron. Our measurements can be used to constrain models, inform future experimental studies of enol reactivity, and potentially enhance current understanding of combustion and environmental chemistry. (c) 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Rapid molecular-weight growth of hydrocarbons occurs in flames, in industrial synthesis, and potentially in cold astrochemical environments. A variety of high- and low-temperature chemical mechanisms have been proposed and confirmed, but more facile pathways may be needed to explain observations. We provide laboratory confirmation in a controlled pyrolysis environment of a recently proposed mechanism, radical-radical chain reactions of resonance-stabilized species. The recombination reaction of phenyl (c-C6H5) and benzyl (c-C6H5CH2) radicals produces both diphenylmethane and diphenylmethyl radicals, the concentration of the latter increasing with rising temperature. A second phenyl addition to the product radical forms both triphenylmethane and triphenylmethyl radicals, confirming the propagation of radical-radical chain reactions under the experimental conditions of high temperature (1100-1600 K) and low pressure (ca. 3 kPa). Similar chain reactions may contribute to particle growth in flames, the interstellar medium, and industrial reactors.

Utilizing highly cascaded harmonic generation, we upconvert a MHz fiber laser to the vacuum ultraviolet (up to 18 eV). We apply the source to combustion-chemistry experiments and conduct numerical simulation to understand the nonlinear generation process.

An ideal vacuum ultraviolet light source for applications in angle-resolved photoemission spectroscopy and photoionization mass spectrometry would have a high flux, a MHz repetition rate, a photon energy range from the UV to at least 15 eV, and variable energy and time resolution. This year, we reported a highly cascaded harmonic generation technique that addresses this challenge.

Vacuum ultraviolet (VUV) light is critical for the study of molecules and materials, but the generation of femtosecond pulses in the VUV region at high repetition rates has proven difficult. Here, we demonstrate the efficient generation of VUV light at MHz repetition rates using highly cascaded four-wave mixing processes in a negative-curvature hollow-core fiber. Both even and odd order harmonics are generated up to the 15th harmonic (69 nm, 18.0 eV), with high energy resolution of ~40 meV. In contrast to direct high harmonic generation, this highly cascaded harmonic generation process requires lower peak intensity and therefore can operate at higher repetition rates, driven by a robust ~10 W fiber-laser system in a compact setup. Additionally, we present numerical simulations that explore the fundamental capabilities and spatiotemporal dynamics of highly cascaded harmonic generation. This VUV source can enhance the capabilities of spectroscopies of molecular and quantum materials, such as photoionization mass spectrometry and time , angle , and spin-resolved photoemission.

Using a cascaded four-wave-mixing process in negative-curvature fibers, we produce high-flux, high-rep-rate femtosecond pulses of UV and VUV light with wavelengths as short as 115 nm, with applications in spectroscopy and materials science.

Light beams carrying orbital angular momentum (OAM) are well known due to their powerful capabilities for applications in many fields, such as optical communications, microscopy, quantum optics, quantum information or microparticle manipulation. In this work we introduce a new class of light beams that possess a unique property associated with a temporal variation of their OAM: the self-torque of light. Despite the recent progress in the generation of designer ultrafast light waveforms with OAM, up to now there is no evidence for the creation of pulses with time-dependent OAM in any spectral regime. We define the self-torque of light as ħξ = ħdℓ(t)/dt, where ħℓ(t) represents the inherent time-variation of a beam's OAM. This definition has an analogy with mechanical systems that self-induce a variation of their angular momentum.

Light fields carrying orbital angular momentum (OAM) provide powerful capabilities for applications in optical communications, microscopy, quantum optics, and microparticle manipulation. We introduce a property of light beams, manifested as a temporal OAM variation along a pulse: the self-torque of light. Although self-torque is found in diverse physical systems (i.e., electrodynamics and general relativity), it was not realized that light could possess such a property. We demonstrate that extreme-ultraviolet self-torqued beams arise in high-harmonic generation driven by time-delayed pulses with different OAM. We monitor the self-torque of extreme-ultraviolet beams through their azimuthal frequency chirp. This class of dynamic-OAM beams provides the ability for controlling magnetic, topological, and quantum excitations and for manipulating molecules and nanostructures on their natural time and length scales.