Photoelectron Photoion Coincidence Research Articles

The N+ Formation Mechanism of Vibrationally Selected N2O+ Ions in the C2Σ+ State: A TPEPICO Imaging Study.

The N-NO bond fission of N2O+(C2Σ+) ions can produce two major fragment ions, NO+ or N+. In contrast to the dominant NO+ fragment ion, the N+ formation mechanism remains unclear to date. Here, dissociative photoionization of N2O via the C2Σ+ ionic state has been reinvestigated using a combined approach of threshold photoelectron-photoion coincidence (TPEPICO) velocity imaging and quantum chemical calculations. Accompanying the N+(3P) formation, the NO(X2Π) neutral fragment with low and high vi-rotational distributions was identified, based on the N+ speed and angular distributions derived from the TPEPICO images. In particular, the excitation of the symmetric stretching ν1+ mode promotes the formation of high rotational components, while the asymmetric stretching ν3+ mode shows the exact opposite effect. According to our calculated multistate potential energy surfaces, intersystem crossing from C2Σ+ to 14Π exclusively provides feasible decomposition pathways to produce the N+ fragment. In a slightly bent geometry, spin-orbit couplings between C2Σ+ and two substates of 14Π, 14A' or 14A″, play a crucial role in the N+ formation from vibrationally selected N2O+(C2Σ+) ions. The mechanism also provides new insights into the charge transfer reaction of N+ + NO → N + NO+.

Photoionization and Dissociative Photoionization of Acetaldehyde in the 10.0-13.7 eV Range by Synchrotron Photoelectron Photoion Coincidence Spectroscopy.

Photoionization and dissociative photoionization of acetaldehyde (CH3CHO) in the 10.0-13.7 eV energy range are studied by using synchrotron radiation double imaging photoelectron photoion coincidence spectroscopy (i2PEPICO). The X2A' and A2A" electronic states of CH3CHO+ as well as the Franck-Condon gap region between these two states have been populated with several vibrational sequences and assigned in the high-resolution slow photoelectron spectrum (SPES). The adiabatic ionization energies (AIEs) of the X2A' and A2A" states are measured at 10.228±0.006 and 12.52±0.05 eV, respectively. The present results show that the X2A' state is a stable state while the A2A" state is fully dissociative to produce CH3CO+, CHO+ and CH4 + fragment ions. The 0 K appearance energies (AE0K) of CH3CO+ and CHO+ fragment ions are determined through the modeling of the breakdown diagram, i. e., AE0K(CH3CO+)=10.89±0.01 eV (including a reverse barrier of ~0.19 eV) and AE0K(CHO+)=11.54±0.05 eV. In addition, the dissociation mechanisms of CH3CHO+ including statistical dissociation, direct bond breaking and isomerization are discussed with the support of the calculated dissociation limits and transition state energies.

Fragmentation and charge transfer in cyclic dipeptides with an aromatic side chain induced by VUV radiation

The fragmentation of three cyclic dipeptides (c-Glycil-Phenylalanine, c-Tryptophan-Tyrosine and c-Tryptophan-Tryptophan), characterized by an aromatic side chain, has been investigated by synchrotron radiation and photoelectron-photoion coincidence (PEPICO) experiments, assisted by atomistic simulations. The PEPICO experiments show that the charged moiety containing the aromatic side chain is the main fragment in the three samples. The theoretical exploration of the potential energy surfaces has allowed to identify the possible fragmentation paths leading to the formation of these fragments. Then, the analysis of the differences in the electronic density distributions of the neutral molecule and the cation and a molecular dynamics simulation provided an understanding of the preferred localization of the positive charge on the aromatic side chain of the cyclic dipeptide.

UV photolysis of oxalyl chloride: ClCO radical decomposition and direct Cl2${\rm Cl}_2 {\rm }$ formation pathways

AbstractOxalyl chloride, , is widely used as a photolytic source of Cl atoms in reaction kinetics studies. photolysis is typically assumed to produce Cl atoms with an overall yield of 2 via three‐body dissociation, , followed by fast subsequent ClCO unimolecular decomposition of either the energetically excited fragment, , or the thermalized ClCO radical, . However, a study by Huang et al. (J. Phys. Chem. A 121 (2017) 2888–2895) found that UV photolysis of at directly yields with a photolysis quantum yield of . This new product pathway may complicate the use of as a clean source of Cl atoms and challenges the previously accepted photodissociation scheme. The purpose of the present work was 2‐fold. Firstly, the unimolecular decomposition of and ClCO radicals has been investigated in / gas mixtures after UV photolysis at and . Cl atoms were captured by added in excess such that concentration‐time profiles of HCl measured by means of mid‐infrared frequency modulation spectroscopy reflect the temporally separated Cl formation pathways. The low‐pressure thermal ClCO decomposition rate constant was determined to be at , which is in very good agreement with previously reported literature values. Secondly, the photolysis quantum yield of direct formation from photofragmentation was studied with time‐of‐flight mass spectrometry using a photoelectron photoion coincidence setup. Calibrated concentration‐time profiles were recorded and analyzed using kinetic simulations accounting for both direct and secondary formation of from photolysis and reactions involving Cl, ClCO, and , respectively. Direct formation could be confirmed, where wavelength‐dependent quantum yields of , , and at , , and were determined. Complementary quantum‐chemical calculations of the potential energy diagram for ground‐state photodissociation reveal a low‐lying energy barrier for the formation of phosgene, . We suggest that subsequent and Cl formation from energetically excited may actually play a role for the overall photodissociation of .

Dissociative photoionization of phenyl triflate, a photoacid generator for photolithography, at 92 eV.

The dissociative photoionization of phenyl triflate (C6H5OSO2CF3), a neutral photoacid generator used in photolithography, was investigated in a gas phase experiment employing extreme ultraviolet (EUV) synchrotron radiation at 92eV and photoelectron-photoion coincidence detection. The interaction of EUV photons with the molecule leads almost exclusively to dissociation, which is dominated by a sequential fragmentation mechanism, in which SO2, CF3, CO, and C2H2 are lost. For lithographic purposes, the lack of the observation of a fragment that could serve as a precursor for the formation of triflic acid means that the effective photoacid generator concentration in a photoresist is reduced, impacting its patterning performance in EUV lithography. A better understanding of the dissociative photoionization of photoresist components and proxies thereof can provide a crucial handle that guides the design of photoresists for the upcoming technology nodes with ever decreasing feature sizes for more powerful computer chips.

CO Cofeeding Affects Product Distribution in CH3Cl Coupling over ZSM‐5 Zeolite: Pressure Twists the Plot

AbstractC1 coupling reactions over zeolite catalysts are central to sustainable chemical production strategies. However, questions persist regarding the involvement of CO in ketene formation, and the impact of this elusive oxygenate intermediate on reactivity patterns. Using operando photoelectron photoion coincidence spectroscopy (PEPICO), we investigate the role of CO in methyl chloride conversion to hydrocarbons (MCTH), a prospective process for methane valorization with a reaction network akin to methanol to hydrocarbons (MTH) but without oxygenate intermediates. Our findings reveal the transformative role of CO in MCTH at the low pressures, inducing ketene formation in MCTH and boosting olefin production, confirming the Koch carbonylation step in the initial stages of C1 coupling. We uncover pressure‐dependent product distributions driven by CO‐induced ketene formation, and its subsequent desorption from the zeolite surface, which is enhanced at low pressure. Inspired by the above results, extension of the co‐feeding approach to CH3OH as another simple oxygenate showcases the additional potential for improved catalyst stability in MCTH at ambient pressure.

Conformer-Specific Photoelectron Spectroscopy of Carbonic Acid: H2CO3.

Carbonic acid (H2CO3) is a fundamental species in biological, ecological, and astronomical systems. However, its spectroscopic characterization is incomplete because of its reactive nature. The photoionization (PI) and the photoion mass-selected threshold photoelectron (ms-TPE) spectra of H2CO3 were obtained by utilizing vacuum ultraviolet (VUV) synchrotron radiation and double imaging photoelectron photoion coincidence spectroscopy. Two carbonic acid conformers, namely, cis-cis and cis-trans, were identified. Experimental adiabatic ionization energies (AIEs) of cis-cis and cis-trans H2CO3 were determined to be 11.27 ± 0.02 and 11.18 ± 0.03 eV, and the cation enthalpies of formation could be derived as ΔfH°0K = 485 ± 2 and 482 ± 3 kJ mol-1, respectively. The cis-cis conformer shows intense peaks in the ms-TPES that are assigned to the C=O/C-OH stretching mode, while the cis-trans conformer exhibits a long progression to which two C=O/C-OH stretching modes contribute. The TPE spectra allow for the sensitive and conformer-selective detection of carbonic acid in terrestrial experiments to better understand astrochemical reactions.

Vacuum Ultraviolet Single Photon Ionization and Decomposition of 2-Aminopropionitrile in Astrophysical Objects

The molecule 2-aminopropionitrile (2-APN; H3CCH(NH2)CN) is a chiral precursor of the amino acid alanine and could play an important role in the emergence of the homochirality of life. To date, 2-APN has not yet been detected in the interstellar medium. To address the question of its absence, possibly through destruction by vacuum ultraviolet radiation in astrophysical media, we studied its photoionization and dissociative photoionization in the 9–14 eV (89–137 nm) energy range using photoelectron–photoion coincidence spectroscopy with velocity map imaging. Density functional theory calculations were performed at the PBE0/aug-cc-pVTZ level to determine structures for the various cationic fragments identified experimentally. Their appearance energies were calculated. The adiabatic ionization energy (AIE) of 2-APN is AIE = (9.85±0.01) eV and the appearance energy (AE) of the major fragment ion N≡CC(H)NH2 + is AE = (10.57±0.01) eV. Both ions, 2-APN+ and N≡CC(H)NH2 +, make up more than 90% of the formed ions. N≡CC(H)NH2 +, an isomer of the protonated HCN dimer, is also formed with high yield in the dissociative photoionization of aminoacetonitrile (NH2CH2CN), another α-aminonitrile observed in Sgr B2(N). Photoion yield spectra have been calibrated to absolute ionization cross sections. From these, we derive photoionization rates in several typical radiation fields relevant to different astrophysical objects. The rates show that, under almost all explored radiation fields, dissociative ionization is the dominant pathway for photoionization, leading to the loss of a methyl group (CH3) to form the planar thermodynamically stable amino cyano methylidynium ion N≡CC(H)NH2 +. The observed absence of 2-APN in Sgr B2 could thus be due to dominant dissociative photoionization.

Gas Phase Ionization Energy of Heptacene.

The ionization energy is a fundamental property that is relevant to charge transport in organic semiconductors. We report adiabatic ionization energies (AIEs) of heptacene at 6.21 and 7.20 eV for the X̃+B2g and Ã+Au states, respectively, as the next larger member of the acene series using mass- and isomer-selective double imaging photoelectron photoion coincidence spectroscopy. The X̃+ state energy decreases monotonically with an increase in size within the homologous series of acenes and approaches an asymptotic limit [AIE(polyacene) = 5.94 ± 0.06 eV] based on a fit with an exponential decay function. As byproducts of heptacene formation from cycloreversion of diheptacenes, 5,18-, 7,16-, and 6,17-dihydroheptacene can be detected, and their AIE is similar to that of their largest acene subunit (anthracene and tetracene, respectively), in very good agreement with computational treatments.

What a difference a chlorine makes: The remarkable unimolecular ion chemistry of phenyl formate and phenyl chloroformate.

Imaging photoelectron photoion coincidence (iPEPICO) spectroscopy and tandem mass spectrometry were employed to explore the ionisation and dissociative ionisation of phenyl formate (PF) and phenyl chloroformate (PCF). The threshold photoelectron spectra of both compounds are featureless and lack a definitive origin transition, owing to the internal rotation of the formate functional group relative to the benzene ring, active upon ionisation. CBS-QB3 calculations yield ionisation energies of 8.88 and 9.03 eV for PF and PCF, respectively. Ionised PF dissociates by the loss of CO via a transition state composed of a phenoxy cation and HCO moieties. The dissociation of PCF ions involves the competing losses of CO (m/z 128/130), Cl (m/z 121) and CO2 (m/z 112/114), with Cl loss also shown to occur from the second excited state in a non-statistical process. The primary CO- and Cl-loss fragment ions undergo sequential reactions leading to fragment ions at m/z 98 and 77. The mass-analysed ion kinetic energy (MIKE) spectrum of PCF+ showed that the loss of CO2 occurs with a large reverse energy barrier, which is consistent with the computationally derived minimum energy reaction pathway.

Evidencing an elusive conical intersection in the dissociative photoionization of methyl iodide.

The valence-shell dissociative photoionization of methyl iodide (CH3I) is studied using double imaging photoelectron photoion coincidence (i2 PEPICO) spectroscopy in combination with highly-tunable synchrotron radiation from synchrotron SOLEIL. The experimental results are complemented by new high-level ab initio calculations of the potential energy curves of the relevant electronic states of the methyl iodide cation (CH3I+). An elusive conical intersection is found to mediate internal conversion from the initially populated first excited state, CH3I+(Ã2A1), into the ground cationic state, leading to the formation of methyl ions (CH3+). The reported threshold photoelectron spectrum for CH3+ reveals that the ν5 scissors vibrational mode promotes the access to this conical intersection and hence, the transfer of population. An intramolecular charge transfer takes place simultaneously, prior to dissociation. Upon photoionization into the second excited cationic state, CH3I+(B̃2E), a predissociative mechanism is shown to lead to the formation of atomic I+.

Gas-phase preparation of the dibenzo[e,l]pyrene (C24H14) butterfly molecule via a phenyl radical-mediated ring annulation.

A high temperature phenyl-mediated addition-cyclization-dehydrogenation mechanism to form peri-fused polycyclic aromatic hydrocarbon (PAH) derivatives-illustrated through the formation of dibenzo[e,l]pyrene (C24H14)-is explored through a gas-phase reaction of the phenyl radical (C6H5˙) with triphenylene (C18H12) utilizing photoelectron photoion coincidence spectroscopy (PEPICO) combined with electronic structure calculations. Low-lying vibrational modes of dibenzo[e,l]pyrene exhibit out-of-plane bending and are easily populated in high temperature environments such as combustion flames and circumstellar envelopes of carbon stars, thus stressing dibenzo[e,l]pyrene as a strong target for far-IR astronomical surveys.

The Unimolecular Chemistry of Methyl Chloroformate Ions and Neutrals: A Story of Near-Threshold Decomposition.

The near-threshold dissociation of ionized and neutral methyl chloroformate (CH3COOCl, MCF) was explored with imaging photoelectron photoion coincidence spectroscopy. The threshold photoelectron spectrum (TPES) for MCF was acquired for the first time; the large geometry changes upon ionization of MCF result in a broad, poorly defined TPES. Franck-Condon simulations are consistent with an adiabatic ionization energy (IE) of 10.90 ± 0.05 eV. Ionized MCF dissociates by chlorine atom loss at a measured 0 K appearance energy (AE) of 11.30 ± 0.01 eV. Together with the above IE, this AE suggests a reaction barrier of 0.40 ± 0.05 eV, consistent with the SVECV-f12 computational result of 0.41 eV. At higher internal energies, the loss of CH3O• becomes competitive due to its lower entropy of activation. Pyrolysis of neutral MCF formed the anticipated major products CH3Cl + CO2 (R1) and the minor products HCl + CO + CH2O (R2). The thermal decomposition products were identified by their photoion mass-selected threshold photoelectron spectrum (ms-TPES). Possible reaction pathways were explored computationally to confirm the dominant ones: R1 proceeds by a concerted Cl atom migration via a four-membered transition state in agreement with the mechanism proposed in the literature. R2 is a two-step reaction first yielding 2-oxiranone by HCl loss, which then decomposes to CH2O and CO. Kinetic modeling of the neutral decomposition could simulate the observed reactions only if the vibrational temperature of the MCF was assumed not to cool in the expansion.

Enlightening salt: enthalpy of formation of gaseous sodium chloride by photoelectron photoion coincidence spectroscopy

An in-vacuum flash pyrolysis microreactor was used to seed a molecular beam with gaseous sodium chloride. The vapour was ionised with tuneable synchrotron vacuum ultraviolet radiation to determine the 0 K appearance energy of the sodium cation from sodium chloride using photoelectron photoion coincidence spectroscopy. In addition to the Na+ and NaCl+ peaks, Na2Cl+ was also observed in the mass spectrum, as a tracer for gaseous (NaCl)2. Larger clusters were not observed. The breakdown diagram showed that the monomer underwent significant collisional cooling in the molecular beam, tentatively because of the increased stagnation pressure in the reactor. It also yielded an Na+ appearance energy of E 0 = 9.351 ± 0.007 eV. By the ion cycle, this leads to D 0(NaCl) = 406.4 ± 0.7 kJ mol−1 and Δf H o⦵ 0K(NaCl(g)) = −179.0 ± 1.0 kJ mol−1, which agree with but are better defined than the previous values. This enthalpy of formation is independent of the crystalline phase, and therefore confirms the literature sublimation enthalpy, as well.

In search of universalities in the dissociative photoionization of PANHs via isomerizations.

In search of the cause behind the similarities often seen in the fragmentation of PANHs, vacuum ultraviolet (VUV) photodissociation of two pairs of isomers quinoline-isoquinoline and 2-naphthylamine-3-methyl-quinoline are studied using the velocity map imaging technique. The internal energy dependence of all primary fragmentation channels is obtained for all four target molecules. The decay dynamics of the four molecules is studied by comparing their various experimental signatures. The dominant channel for the first pair of isomers is found to be hydrogen cyanide (HCN) neutral loss, while the second pair of isomers lose HCNH neutral as its dominant channel. Despite this difference in their primary decay products and the differences in the structures of the four targets, various similarities in their experimental signatures are found, which could be explained by isomerization mechanisms to common structures. The fundamental role of these isomerization in controlling different dissociative channels is explored via a detailed analysis of the experimental photoelectron-photoion coincidences and the investigation of the theoretical potential energy surface. These results add to the notion of a universal PANH fragmentation mechanism and suggests the seven member isomerization as a key candidate for this universal mechanism. The balance between isomerization, dissociation, and other key mechanistic processes in the reaction pathways, such as hydrogen migrations, is also highlighted for the four molecules.

Dopant ionization and efficiency of ion and electron ejection from helium nanodroplets.

Photoionization spectroscopy and mass spectrometry of doped helium (He) nanodroplets rely on the ability to efficiently detect ions and/or electrons. Using a commercial quadrupole mass spectrometer and a photoelectron-photoion coincidence spectrometer, we systematically measure yields of ions and electrons created in pure and doped He nanodroplets in a wide size range and in two ionization regimes-direct ionization and secondary ionization after resonant photoexcitation of the droplets. For two different types of dopants (oxygen molecules, O2, and lithium atoms, Li), we infer the optimal droplet size to maximize the yield of ejected ions. When dopants are ionized by charge-transfer to photoionized He nanodroplets, the highest yield of O2 and Li ions is detected for a mean size of ∼5×104 He atoms per nanodroplet. When dopants are Penning ionized via photoexcitation of the He droplets, the highest yield of O2 and Li ions is detected for ∼103 and ∼105 He atoms per droplet, respectively. At optimum droplet sizes, the detection efficiency of dopant ions in proportion to the number of primary photoabsorption events is up to 20% for charge-transfer ionization of O2 and 2% for Li, whereas for Penning ionization it is 1% for O2 and 4% for Li. Our results are instrumental in determining optimal conditions for mass spectrometric studies and photoionization spectroscopy of molecules and complexes isolated in He nanodroplets.

Revealing Active Sites and Reaction Pathways in Methane Non-Oxidative Coupling over Iron-Containing Zeolites.

Non-oxidative coupling of methane is a promising route to obtain ethylene directly from natural gas. We synthesized siliceous [Fe]zeolites with MFI and CHA topologies and found that they display high selectivity (>90 % for MFI and >99 % for CHA) to ethylene and ethane among gas-phase products. Deactivated [Fe]zeolites can be regenerated by burning coke in air. In situ X-ray absorption spectroscopy demonstrates that the isolated Fe3+ centers in zeolite framework of fresh catalysts are reduced during the reaction to the active sites, including Fe2+ species and Fe (oxy)carbides dispersed in zeolite pores. Photoelectron photoion coincidence spectroscopy results show that methyl radicals are the reaction intermediates formed upon methane activation. Ethane is formed by methyl radical coupling, followed by its dehydrogenation to ethylene. Based on the observation of intermediates including allene, vinylacetylene, 1,3-butadiene, 2-butyne, and cyclopentadiene over [Fe]MFI, a reaction network is proposed leading to polyaromatic species. Such reaction intermediates are not observed over the small-pore [Fe]CHA, where ethylene and ethane are the only gas-phase products.

Revealing Active Sites and Reaction Pathways in Methane Non‐Oxidative Coupling over Iron‐Containing Zeolites

AbstractNon‐oxidative coupling of methane is a promising route to obtain ethylene directly from natural gas. We synthesized siliceous [Fe]zeolites with MFI and CHA topologies and found that they display high selectivity (>90 % for MFI and >99 % for CHA) to ethylene and ethane among gas‐phase products. Deactivated [Fe]zeolites can be regenerated by burning coke in air. In situ X‐ray absorption spectroscopy demonstrates that the isolated Fe3+ centers in zeolite framework of fresh catalysts are reduced during the reaction to the active sites, including Fe2+ species and Fe (oxy)carbides dispersed in zeolite pores. Photoelectron photoion coincidence spectroscopy results show that methyl radicals are the reaction intermediates formed upon methane activation. Ethane is formed by methyl radical coupling, followed by its dehydrogenation to ethylene. Based on the observation of intermediates including allene, vinylacetylene, 1,3‐butadiene, 2‐butyne, and cyclopentadiene over [Fe]MFI, a reaction network is proposed leading to polyaromatic species. Such reaction intermediates are not observed over the small‐pore [Fe]CHA, where ethylene and ethane are the only gas‐phase products.

Ultrastable, high-repetition-rate attosecond beamline for time-resolved XUV–IR coincidence spectroscopy

The implementation of attosecond photoelectron–photoion coincidence spectroscopy for the investigation of atomic and molecular dynamics calls for a high-repetition-rate driving source combined with experimental setups characterized by excellent stability for data acquisition over time intervals ranging from a few hours up to a few days. This requirement is crucial for the investigation of processes characterized by low cross sections and for the characterization of fully differential photoelectron(s) and photoion(s) angular and energy distributions. We demonstrate that the implementation of industrial-grade lasers, combined with a careful design of the delay line implemented in the pump–probe setup, allows one to reach ultrastable experimental conditions leading to an error in the estimation of the time delays of only 12 as over an acquisition time of 6.5 h. This result opens up new possibilities for the investigation of attosecond dynamics in simple quantum systems.

Direct Observation of the Ethyl Radical in the Pyrolysis of Ethane.

We report the first direct detection of ethyl radical in the pyrolysis of ethane. Observation of this vital intermediate was made possible in this extremely reactive environment by the use of a microreactor coupled with synchrotron radiation and photoelectron photoion coincidence (PEPICO) spectroscopy, despite its short lifetime and low concentration. Together with ab-initio master equation-calculated rates and fully coupled computational fluid dynamics simulations, our measurements show that even under the low pressures and short residence times in our experiment, ethyl formation can only be explained by bimolecular reactions; the most important is the catalytic attack of ethane by H atoms, which are then regenerated by decomposition of the nascent ethyl radicals. Our results complete the observation of all hypothesized intermediates in this industrially important process and highlight the need for further studies under additional conditions using similar methods to improve existing models and optimize process chemistries.