skip to main content


Title: 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 C 6 H 6 ) 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 C 6 H 6 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.  more » « less
Award ID(s):
1665464
NSF-PAR ID:
10382703
Author(s) / Creator(s):
; ; ; ; ;
Date Published:
Journal Name:
Faraday Discussions
Volume:
238
ISSN:
1359-6640
Page Range / eLocation ID:
645 to 664
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. The kinetics of the combustion-relevant reaction of the allyl radical, a-C 3 H 5 , with molecular oxygen has been studied in a flow tube reactor at the vacuum ultraviolet (VUV) beamline of the Swiss Light Source storage ring, using the CRF-PEPICO (Combustion Reactions Followed by Photoelectron Photoion Coincidence Spectroscopy) setup. The ability to measure threshold photoelectron spectra enables a background-free detection of reactive species as well as an isomer-specific analysis of reaction products. Allyl was generated by direct photodissociation of allyl iodide at 266 nm and 213 nm and indirectly by the reaction of propene with Cl atoms, which were generated by photolysis from oxalyl chloride at 266 nm. Experiments were conducted at room temperature at low pressures between 0.8 and 3 mbar using Ar as the buffer gas and with excess O 2 to maintain nearly pseudo-first-order reaction conditions. Whereas allyl was detected by photoionisation using synchrotron radiation, the main reaction product allyl peroxy was not observed due to dissociative ionisation of this weakly bound species. From the concentration–time profiles of the allyl signal, second-order rate constants between 1.35 × 10 11 cm 3 mol −1 s −1 at 0.8 mbar and 1.75 × 10 11 cm 3 mol −1 s −1 at 3 mbar were determined. The rates obtained for the different allyl radical generation schemes agree well with each other, but are about a factor of 2 higher than the ones reported previously using He as a buffer gas. The discrepancy is partly attributed to the higher collision efficiency of Ar causing a varying fall-off behavior. When allyl is produced by the reaction of propene with Cl atom, an unexpected product is observed at m / z = 68, which was identified as 1,3-butadienal in the threshold photoelectron spectrum. It is formed in a secondary reaction of allyl with the OCCl radical, which is generated in the 266 nm photolysis of oxalyl chloride. 
    more » « less
  2. null (Ed.)
    Coincidence ion pair production (cipp) spectra of F 2 were recorded on the DELICIOUS III coincidence spectrometer in the one-photon excitation region of 125 975–126 210 cm −1 . The F + + F − signal shows a rotational band head structure, corresponding to F 2 Rydberg states crossing over to the ion pair production surface. Spectral simulation and quantum defect analysis allowed the characterization of five new molecular Rydberg states (F 2 **): one Π and four Σ states. The lowest-energy Rydberg state spectrum observed ( T 0 = 125 999 cm −1 ) lacked some of the predicted rotational structure, which allowed an accurate determination of the ion pair production threshold of 15.6229 4 ± 0.0004 3 eV. Using the well-known atomic fluorine ionization energy and electron affinity, this number leads to a ground state F–F dissociation energy of 1.6012 9 ± 0.0004 4 eV. Photoelectron photoion coincidence (PEPICO) experiments were also carried out on F 2 and the dissociative photoionization threshold to F + + F was determined as 19.0242 ± 0.0006 eV. Using the atomic fluorine ionization energy, this can be converted to an F 2 dissociation energy of 1.6013 2 ± 0.0006 2 eV, further confirming the cipp-derived value above. Because the two experiments were independently energy-calibrated, they can be averaged to 1.6013 0 ± 0.0003 6 eV and this value can be used to derive the fluorine atom's 0 K heat of formation as 77.25 1 ± 0.01 7 kJ mol −1 . This latter is in excellent agreement with the latest Active Thermochemical Table (ATcT) value but improves its accuracy by almost a factor of three. 
    more » « less
  3. The valence photoionization of light and deuterated methanol dimers was studied by imaging photoelectron photoion coincidence spectroscopy in the 10.00–10.35 eV photon energy range. Methanol clusters were generated in a rich methanol beam in nitrogen after expansion into vacuum. They generally photoionize dissociatively to protonated methanol cluster cations, (CH 3 OH) n H + . However, the stable dimer parent ion (CH 3 OH) 2 + is readily detected below the dissociation threshold to yield the dominant CH 3 OH 2 + fragment ion. In addition to protonated methanol, we could also detect the water- and methyl-loss fragment ions of the methanol dimer cation for the first time. These newly revealed fragmentation channels are slow and cannot compete with protonated methanol cation formation at higher internal energies. In fact, the water- and methyl-loss fragment ions appear together and disappear at a ca. 150 meV higher energy in the breakdown diagram. Experiments with selectively deuterated methanol samples showed H scrambling involving two hydroxyl and one methyl hydrogens prior to protonated methanol formation. These insights guided the potential energy surface exploration to rationalize the dissociative photoionization mechanism. The potential energy surface was further validated by a statistical model including isotope effects to fit the experiment for the light and the perdeuterated methanol dimers simultaneously. The (CH 3 OH) 2 + parent ion dissociates via five parallel channels at low internal energies. The loss of both CH 2 OH and CH 3 O neutral fragments leads to protonated methanol. However, the latter, direct dissociation channel is energetically forbidden at low energies. Instead, an isomerization transition state is followed by proton transfer from a methyl group, which leads to the CH 3 (H)OH + ⋯CH 2 OH ion, the precursor to the CH 2 OH-, H 2 O-, and CH 3 -loss fragments after further isomerization steps, in part by a roaming mechanism. Water loss yields the ethanol cation, and two paths are proposed to account for m/z 49 fragment ions after CH 3 loss. The roaming pathways are quickly outcompeted by hydrogen bond breaking to yield CH 3 OH 2 + , which explains the dominance of the protonated methanol fragment ion in the mass spectrum. 
    more » « less
  4. We present an ab initio computational study of the Auger electron spectrum of benzene. Auger electron spectroscopy exploits the Auger–Meitner effect, and although it is established as an analytic technique, the theoretical modeling of molecular Auger spectra from first principles remains challenging. Here, we use coupled-cluster theory and equation-of-motion coupled-cluster theory combined with two approaches to describe the decaying nature of core-ionized states: (i) Feshbach–Fano resonance theory and (ii) the method of complex basis functions. The spectra computed with these two approaches are in excellent agreement with each other and also agree well with experimental Auger spectra of benzene. The Auger spectrum of benzene features two well-resolved peaks at Auger electron energies above 260 eV, which correspond to final states with two electrons removed from the 1 e 1 g and 3 e 2 g highest occupied molecular orbitals. At lower Auger electron energies, the spectrum is less well resolved, and the peaks comprise multiple final states of the benzene dication. In line with theoretical considerations, singlet decay channels contribute more to the total Auger intensity than the corresponding triplet decay channels. 
    more » « less
  5. The dissociative photoionization processes of methyl hydroperoxide (CH 3 OOH) have been studied by imaging Photoelectron Photoion Coincidence (iPEPICO) spectroscopy experiments as well as quantum-chemical and statistical rate calculations. Energy selected CH 3 OOH + ions dissociate into CH 2 OOH + , HCO + , CH 3 + , and H 3 O + ions in the 11.4–14.0 eV photon energy range. The lowest-energy dissociation channel is the formation of the cation of the smallest “QOOH” radical, CH 2 OOH + . An extended RRKM model fitted to the experimental data yields a 0 K appearance energy of 11.647 ± 0.005 eV for the CH 2 OOH + ion, and a 74.2 ± 2.6 kJ mol –1 mixed experimental-theoretical 0 K heat of formation for the CH 2 OOH radical. The proton affinity of the Criegee intermediate, CH 2 OO, was also obtained from the heat of formation of CH 2 OOH + (792.8 ± 0.9 kJ mol –1 ) to be 847.7 ± 1.1 kJ mol –1 , reducing the uncertainty of the previously available computational value by a factor of 4. RRKM modeling of the complex web of possible rearrangement-dissociation processes were used to model the higher-energy fragmentation. Supported by Born–Oppenheimer molecular dynamics simulations, we found that the HCO + fragment ion is produced through a roaming transition state followed by a low barrier. H 3 O + is formed in a consecutive process from the CH 2 OOH + fragment ion, while direct C–O fission of the molecular ion leads to the methyl cation. 
    more » « less