Mass-selected Threshold Photoelectron Spectroscopy Research Articles

N-Carbazolyl π-Radical and Its Antiaromatic Nitrenium Ion: A Threshold Photoelectron Spectroscopic Study.

Understanding the structure and properties of heterocyclic radicals and their cations is crucial for elucidating reaction mechanisms as they serve as versatile synthetic intermediates. In this work, the N-carbazolyl radical 1 was generated via pyrolysis and characterized using photoion mass-selected threshold photoelectron spectroscopy coupled with tunable vacuum-ultraviolet synchrotron radiation. The N-centered radical 1 is classified as a π-radical (2B1), with the unpaired electron found to be delocalized over the central five-membered ring of the carbazole. Adiabatic ionization energies corresponding to the transition from radical 1 to its singlet 1+(1A1) and triplet 1+(3B2) cations were determined to be 7.70 ± 0.03 and 8.14 ± 0.03 eV, respectively. The antiaromatic nitrenium ion 1+ exhibits a singlet ground state with an experimental singlet-triplet energy gap (ΔES-T) of -0.44 eV (10.1 kcal/mol), in very good agreement with theory. N-centered radicals are found to have a higher ionization energy than their C-centered analogues due to stabilization of the singly occupied molecular orbital.

The isomer distribution of C6H6 products from the propargyl radical gas-phase recombination investigated by threshold-photoelectron spectroscopy

The resonance-stabilization of the propargyl radical (C3H3) makes it among the most important reactive intermediates in extreme environments and grants it a long enough lifetime to recombine in both terrestrial combustion media and cold molecular clouds in space. This makes the propargyl self-reaction a pivotal step in the formation of benzene, the first aromatic ring, to eventually lead to polycyclic aromatic hydrocarbons in a variety of environments. In this work, by producing propargyl radicals in a flow tube where propyne reacted with F atoms and probing the reaction products by mass-selected threshold-photoelectron spectroscopy (TPES), we identified eight C6H6 products in total, including benzene. On top of providing the first comprehensive measurements of the branching ratios of the eight identified C6H6 isomers in the propargyl self reaction products (4 mbar, 298 K conditions), this study also highlights the advantages and disadvantages of using isomer-selective TPES to identify and quantify reaction products.

Threshold photoelectron spectroscopy of organosulfur radicals.

We report vibrationally resolved threshold photoelectron spectra of several sulfur-containing reactive intermediates. This includes the organosulfur radicals CH2S, CH3S, CH2SH, CH3S2, and S2H, which are relevant in atmospheric chemistry and in astrochemical settings. Due to the high reactivity, the radicals were prepared in situ via pyrolysis of (CH3)2S2. The organosulfur species were characterized by photoion mass-selected threshold photoelectron spectroscopy, employing the photoelectron-photoion coincidence setup (PEPICO) and synchrotron radiation from the Swiss Light Source. We report improved ionization energies and characterize ionic ground and excited states, both singlet and triplet. The vibrational structure was simulated based on computed geometries and vibrational frequencies, giving insight into the geometry change upon ionization.

Formation of five-membered ring structures via reactions of o-benzyne

The formation of five-membered ring structures is important for the generation of curved and bowl-shaped polycyclic aromatic hydrocarbons (PAHs) under combustion conditions. Here, we report the identification of the indenyl (C9H7) radical – the simplest aromatic hydrocarbon radical carrying an adjacent five- and six-membered ring, as the major product of the o-benzyne (o-C6H4) reaction with propargyl (C3H3). Because real flames exhibit a complex chemistry, elucidation of a specific reaction is very challenging. Instead, we studied the o-C6H4 + C3H3 reaction in a resistively heated microtubular SiC reactor at controlled conditions of 1150 K and a pressure near 10–20 Torr. To this end, the reactants o-benzyne and propargyl were pyrolytically generated from benzoyl chloride and propargyl bromide. We identified the reactants and the indenyl radical isomer-selectively utilizing photoion mass-selected threshold photoelectron spectroscopy (ms-TPES). The experimentally observed predominant formation of indenyl radicals finally confirms the theoretical predictions of Matsugi and Miyoshi [Phys. Chem. Chem. Phys. 14 (2012), 9722–9728] and highlights a versatile route for the formation of five-membered rings and curved PAHs via reactions of o-benzyne that favor the formation of multiring species over aliphatically substituted aromatic species.

The elusive phenylethynyl radical and its cation: synthesis, electronic structure, and reactivity.

Alkynyl radicals and cations are crucial reactive intermediates in chemistry, but often evade direct detection. Herein, we report the direct observation of the phenylethynyl radical (C6H5CC˙) and its cation (C6H5CC+), which are two of the most reactive intermediates in organic chemistry. The radical is generated via pyrolysis of (bromoethynyl)benzene at temperatures above 1500 K and is characterized by photoion mass-selected threshold photoelectron spectroscopy (ms-TPES). Photoionization of the phenylethynyl radical yields the phenylethynyl cation, which has never been synthesized due to its extreme electrophilicity. Vibrationally-resolved ms-TPES assisted by ab initio calculations unveiled the complex electronic structure of the phenylethynyl cation, which appears at an adiabatic ionization energy (AIE) of 8.90 ± 0.05 eV and exhibits an uncommon triplet (3B1) ground state, while the closed-shell singlet (1A1) state lies just 2.8 kcal mol-1 (0.12 eV) higher in energy. The reactive phenylethynyl radical abstracts hydrogen to form ethynylbenzene (C6H5CCH) but also isomerizes via H-shift to the o-, m-, and p-ethynylphenyl isomers (C6H4CCH). These radicals are very reactive and undergo ring-opening followed by H-loss to form a mixture of C8H4 triynes, along with low yields of cyclic 3- and 4-ethynylbenzynes (C6H3CCH). At higher temperatures, dehydrogenation from the unbranched C8H4 triynes forms the linear tetraacetylene (C8H2), an astrochemically relevant polyyne.

Cyclopentene and cyclopentadiene formation in isoprene pyrolysis.

Photoion mass-selected threshold photoelectron spectroscopy (ms-TPES) was used to identify the isoprene pyrolysis products in a SiC microreactor at 1400 °C with the help of literature and Franck-Condon simulated reference spectra for molecular species at the detected m/z ratios. The key observation is the presence of equimolar amounts of isoprene and cyclopentene at the pyrolysis temperature based on the m/z 68 ms-TPES, indicating kinetically allowed isoprene isomerization concurrently with fragmentation reactions. This isomerization was computationally explored and was found to take place via a short-lived vinylcyclopropane intermediate, which was previously proposed to isomerize into isoprene and cyclopentene, with the latter product being dominant. Cyclopentene then decomposes by loss of H2 to form m/z 66, cyclopentadiene (also observed). Previously postulated products of dimethylallene, methylallene, and allene were not observed. Of the possible C2-C4-products, the extracted ms-TPES confirmed only 1,3-butadiene and 2-butyne (m/z 54), 1-buten-3-yne (m/z 52), propene (m/z 42), propyne (m/z 40), propargyl radical (m/z 39), as well as C2H4, C2H2, CH4, and CH3. A trace amount of benzene was also observed at m/z 78, indicative of bimolecular chemistry. The results draw into question a number of the suggested unimolecular reaction products in the recent literature and thus the kinetic models for isoprene pyrolysis.

Photoion Mass-Selected Threshold Photoelectron Spectroscopy to Detect Reactive Intermediates in Catalysis: From Instrumentation and Examples to Peculiarities and a Database.

Photoion mass-selected threshold photoelectron spectroscopy (ms-TPES) is a synchrotron-based, universal, sensitive, and multiplexed detection tool applied in the areas of catalysis, combustion, and gas-phase reactions. Isomer-selective vibrational fingerprints in the ms-TPES of stable and reactive intermediates allow for unequivocal assignment of spectral carriers. Case studies are presented on heterogeneous catalysis, revealing the role of ketenes in the methanol-to-olefins process, the catalytic pyrolysis mechanism of lignin model compounds, and the radical chemistry upon C-H activation in oxyhalogenation. These studies demonstrate the potential of ms-TPES as an analytical technique for elucidating complex reaction mechanisms. We examine the robustness of ms-TPES assignments and address sampling effects, especially the temperature dependence of ms-TPES due to rovibrational broadening. Data acquisition approaches and the Stark shift from the extraction field are also considered to arrive at general recommendations. Finally, the PhotoElectron PhotoIon Spectral Compendium (https://pepisco.psi.ch), a spectral database hosted at Paul Scherrer Institute to support assignment, is introduced.

Unimolecular isomerisation of 1,5-hexadiyne observed by threshold photoelectron photoion coincidence spectroscopy.

The unimolecular isomerisation of the prompt propargyl + propargyl "head-to-head" adduct, 1,5-hexadiyne, to fulvene and benzene by the 3,4-dimethylenecyclobut-1-ene (DMCB) intermediate (all C6H6) was studied in the high-pressure limit by threshold photoelectron (TPE) spectroscopy. TPE spectra (TPES) were recorded with photoelectron photoion coincidence spectroscopy using synchrotron vacuum ultraviolet radiation. Reference TPES, obtained using pure compounds or judiciously extracted from the pyrolysis data, served as basis functions for pyrolysis quantification. From these spectra, we measured a revised fulvene ionisation energy of 8.401 ± 0.005 eV. Temperature-dependent pyrolysis spectra were decomposed using these basis functions. The basis function coefficients were converted to product yields relying on assumed integral threshold photoionisation cross sections obtained by three, partially mutually exclusive sets of assumptions. Thus, the product yields of DMCB, fulvene, and benzene have been established, as well as their uncertainty. The derived mole fractions are consistent with modeling based on the C6H6 potential and RRKM master equation model of Miller and Klippenstein [J. Phys. Chem. A, 2003, 107, 7783]. Although our results are fully consistent with the parallel isomerisation pathways to benzene and fulvene found by Miller and Klippenstein, we observe the onset of fulvene at a lower temperature than that of the onset of benzene, in agreement with the master equation model but in contrast to the previous experiments of Stein et al. [Proc. Combust. Inst., 1990, 23, 85]. This work promotes the use of photoion mass-selected threshold photoelectron spectroscopy as a rapid, sensitive, isomer-selective, and quantitative detection tool among the panoply of established analytical techniques.

Isomer-Selective Threshold Photoelectron Spectra of Phenylnitrene and Its Thermal Rearrangement Products.

The photoionization of phenylnitrene was investigated by photoion mass-selected threshold photoelectron spectroscopy in the gas phase. Flash vacuum pyrolysis of phenyl azide at 480 °C produces the nitrene, which subsequently rearranges at higher temperatures affording three isomeric cyanocyclopentadienes, in contrast to low-temperature trapping experiments. Temperature control of the reactor and threshold photoelectron spectra allows for optimizing the generation of phenylnitrene or its thermal rearrangement products, as well as obtaining vibrational information for the corresponding ions. The adiabatic ionization energies (AIE) of the triplet nitrene (3A2) to the radical cation in its lowest-energy doublet (2B2) and quartet (4A1) spin states were determined to 8.29 ± 0.01 and 9.73 ± 0.01 eV, respectively. Vibrational frequencies of ring breathing modes were measured at 500 ± 80 and 484 ± 80 cm-1 for both the [Formula: see text](2B2) and [Formula: see text](4A1) cationic states, respectively. The AIE differ from the values previously reported; hence, we revise the doublet-quartet energy splitting of the phenylnitrene radical cation to 1.44 eV, in excellent agreement with composite methods and coupled cluster calculations, but considerably higher than the literature reference (1.1 eV).

Decomposition of Picolyl Radicals at High Temperature: A Mass Selective Threshold Photoelectron Spectroscopy Study.

The reaction products of the picolyl radicals at high temperature were characterized by mass‐selective threshold photoelectron spectroscopy in the gas phase. Aminomethylpyridines were pyrolyzed to initially produce picolyl radicals (m/z=92). At higher temperatures further thermal reaction products are generated in the pyrolysis reactor. All compounds were identified by mass‐selected threshold photoelectron spectroscopy and several hitherto unexplored reactive molecules were characterized. The mechanism for several dissociation pathways was outlined in computations. The spectrum of m/z=91, resulting from hydrogen loss of picolyl, shows four isomers, two ethynyl pyrroles with adiabatic ionization energies (IEad) of 7.99 eV (2‐ethynyl‐1H‐pyrrole) and 8.12 eV (3‐ethynyl‐1H‐pyrrole), and two cyclopentadiene carbonitriles with IE′s of 9.14 eV (cyclopenta‐1,3‐diene‐1‐carbonitrile) and 9.25 eV (cyclopenta‐1,4‐diene‐1‐carbonitrile). A second consecutive hydrogen loss forms the cyanocyclopentadienyl radical with IE′s of 9.07 eV (T 0) and 9.21 eV (S1). This compound dissociates further to acetylene and the cyanopropynyl radical (IE=9.35 eV). Furthermore, the cyclopentadienyl radical, penta‐1,3‐diyne, cyclopentadiene and propargyl were identified in the spectra. Computations indicate that dissociation of picolyl proceeds initially via a resonance‐stabilized seven‐membered ring.

Dissociation dynamics of energy-selected ions using threshold photoelectron-photoion coincidence velocity imaging

Threshold photoelectron-photoion coincidence (TPEPICO) is a powerful method to prepare and analyze internal energy- or state-selected ions. Here, we review the state-of-the-art TPEPICO imaging technique combining with tunable vacuum ultraviolet (VUV) synchrotron radiation and its recent applications at Hefei Light Source (HLS), especially on the fundamental data measurement and the dissociation dynamics of ions. By applying the double velocity map imaging for both electrons and ions in coincidence, the collection efficiency of the charged particles, the electron energy resolution and the resolving power of the released kinetic energy in dissociation have been greatly improved. The kinetic energy and the angular distributions of fragment ions dissociated from parent ions with definitive internal energy or state have been acquired directly from TPEPICO images. Some dissociation mechanisms involving non-adiabatic quantum effects, like conical intersection and internal conversion, have been revealed. Moreover, the mass-selected threshold photoelectron spectroscopy (MS-TPES) shows tremendous advantages in isomer-specific analysis of complex systems.

Self-Reaction of ortho-Benzyne at High Temperatures Investigated by Infrared and Photoelectron Spectroscopy.

ortho-Benzyne, a Kekulé-type biradical is considered to be a key intermediate in the formation of polycyclic aromatic hydrocarbons (PAH) and soot. In the present work we study the ortho-benzyne self-reactions in a hot microreactor and identify the high-temperature products by IR/UV spectroscopy and by photoion mass-selected threshold photoelectron spectroscopy (ms-TPES) in a free jet. Ms-TPES confirms formation of ortho-benzyne as generated from benzocyclobutenedione, as well as benzene, biphenylene, diacetylene, and acetylene, originating from the reaction o-C6H4 → HCC-CCH + C2H2, and CH3. PAH molecules like naphthalene, 2-ethynylnaphthalene, fluorene, phenanthrene, and triphenylene are identified based on their IR/UV spectra. By comparison with recent computations their formation starting from o-benzyne can be readily understood and supports the importance of the biradical addition (1,4-cycloaddition followed by fragmentation) pathway to PAH molecules, recently proposed by Comandini et al.

Unimolecular Dissociation of 1-Methylpyrene Cations: Why Are 1-Methylenepyrene Cations Formed and Not a Tropylium-Containing Ion?

1-Methylpyrene radical cations undergo the loss of a hydrogen atom at internal energies above the first dissociation threshold. Imaging photoelectron photoion coincidence spectroscopy was employed in combination with RRKM modeling to determine a 0 K activation energy of 2.78 ± 0.25 eV and an entropy of activation of 6 ± 19 J K-1 mol-1 for this H-loss reaction. The ionization energy of 1-methylpyrene was measured by mass-selected threshold photoelectron spectroscopy to be 7.27 ± 0.01 eV. These values were found to be consistent with calculations at the CCSD/6-31G(d)//B3-LYP/6-31G(d) level of theory showing that the formation of the 1-methylenepyrene cation (resulting from H loss from the methyl group) is kinetically more favorable than the formation of a tropylium-containing product ion that is structurally analogous to the formation of the tropylium cation in H loss from ionized toluene. The shift away from a tropylium-containing structure was found to be due to the increased ring strain imposed on the C7 moiety when it is bound to three fused benzene rings. The RRKM results allow for the derivation of the Δf H0o (1-methylenepyrene cation) of 945 ± 31 kJ mol-1.

The ortho-benzyne cation is not planar.

A recent review on the photoionisation of the C6H4 isomer ortho-benzyne suggests that bands reported in earlier photoelectron spectra might be due to side products or contaminations, while computations raise doubts, whether the cation has a planar geometry. We therefore reinvestigate the photoionisation of ortho-benzyne, generated by pyrolysis from benzocyclobutenedione, by photoion mass-selected threshold photoelectron (ms-TPE) spectroscopy using synchrotron radiation. The experiments are accompanied by a theoretical study that investigates the structure of the ortho-benzyne cation systematically as a function of the computational method, up to CASPT2(11,14) ab initio computations. Our study leads to a re-evaluation of the ionisation energy of ortho-benzyne. It reveals that the ortho-benzyne cation has indeed a twisted C2 geometry rather than a C2v structure. A vertical ionisation energy IEvert of 9.77 eV and an adiabatic ionisation energy of IEad = 9.56 eV are computed for ortho-benzyne. A Franck-Condon simulation of the photoelectron spectrum based on the CASPT2 results and including three electronic states of the cation is in agreement with the experiment and yields IEad = 9.51 eV (+50 meV/-100 meV). Since this value is in contrast with previous work, the ionisation energy has to be revised based on our study. Computational methods based on density functional theory give a reasonable description of the cationic ground state, but fail for the corresponding excited electronic states that are indispensible for a proper assignment of the photoelectron spectrum.

Probing different spin states in xylyl radicals and ions

Resonant one-color two-photon ionization spectroscopy and mass-selected threshold photoelectron spectroscopy were applied to study the electronic doublet states of the three xylyl (methyl-benzyl) radicals above 3.9 eV as well as the singlet and triplet states of the cations up to 10.5 eV. The experiments are complemented by quantum chemical calculations and Franck-Condon simulations to characterize the transitions and to identify the origin bands, allowing a precise determination of singlet-triplet splittings in the cations. Torsional motions of the methyl group notably affect the D0 → D3 transition of m-xylyl. All other investigated transitions either lead to electronic states with very low rotational barriers or suffer from spectral broadening in excess of methyl torsional energy levels. The methyl internal rotational potential is faithfully reproduced with the most basic ab initio methods, yet hyperconjugation could not be identified as a significant force shaping them. Time-dependent density functional theory describes the excited electronic states better than wave function theory approaches, notably EOM-CCSD.

On the formation of cyclopentadiene in the C3H5˙ + C2H2 reaction.

The reaction between the allyl radical (C3H5˙) and acetylene (C2H2) in a heated microtubular reactor has been studied at the VUV beamline of the Swiss Light Source. The reaction products are sampled from the reactor and identified by their photoion mass-selected threshold photoelectron spectra (ms-TPES) by means of imaging photoelectron photoion coincidence spectroscopy. Cyclopentadiene is identified as the sole reaction product by comparison of the measured photoelectron spectrum with that of cyclopentadiene. With the help of quantum-chemical computations of the C5H7 potential energy surface, the C2H2 + C3H5˙ association reaction is confirmed to be the rate determining step, after which H-elimination to form C5H6 is prompt in the absence of re-thermalization at low pressures. The formation of cyclopentadiene as the sole product from the allyl + acetylene reaction offers a direct path to the formation of cyclic hydrocarbons under combustion relevant conditions. Subsequent reactions of cyclopentadiene may lead to the formation of the smallest polycyclic aromatic molecule, naphthalene.

Isomer-Specific Product Detection of Gas-Phase Xylyl Radical Rearrangement and Decomposition Using VUV Synchrotron Photoionization

Xylyl radicals are intermediates in combustion processes since their parent molecules, xylenes, are present as fuel additives. In this study we report on the photoelectron spectra of the three isomeric xylyl radicals and the subsequent decomposition reactions of the o-xylyl radical, generated in a tubular reactor and probed by mass selected threshold photoelectron spectroscopy and VUV synchrotron radiation. Franck-Condon simulations are applied to augment the assignment of elusive species. Below 1000 K, o-xylyl radicals decompose by hydrogen atom loss to form closed-shell o-xylylene, which equilibrates with benzocyclobutene. At higher temperatures relevant to combustion engines, o-xylylene generates styrene in a multistep rearrangement, whereas the p-xylylene isomer is thermally stable, a key point of difference in the combustion of these two isomeric fuels. Another striking result is that all three xylyl isomers can generate p-xylylene upon decomposition. In addition to C8H8 isomers, phenylacetylene and traces of benzocyclobutadiene are observed and identified as further reaction products of o-xylylene, while there is also some preliminary evidence for benzene and benzyne formation. The experimental results reported here are complemented by a comprehensive theoretical C8H8 potential energy surface, which together with the spectroscopic assignments can explain the complex high-temperature chemistry of o-xylyl radicals.