Selective identification of cyclopentaring-fused PAHs and side-substituted PAHs in a low pressure premixed sooting flame by photoelectron photoion coincidence spectroscopy.

This work reports on the selective on-line identification of polycyclic aromatic hydrocarbons (PAHs) formed in a low-pressure methane sooting flame, carried out using the double imaging Photoelectron Photoion Coincidence Spectroscopy method (i2PEPICO) on the DESIRS VUV beamline at the synchrotron SOLEIL. Generally, this work demonstrates the capabilities of the i2PEPICO method to identify PAHs in sooting flames, and in particular to distinguish cyclopentaring-fused PAHs (CP-PAHs) and side-substituted PAHs from their benzenoid isomers. Experimental threshold photoelectron spectra of four CP-PAHs: acenapthylene (C12H8, 152 m/z), acenaphtene (C12H10, 154 m/z), fluoranthene (C16H10, 202 m/z) and benzo(ghi)fluoranthene (C18H10, 226 m/z) are also reported for the first time.

Quantifying the photoionization cross section of the hydroxyl radical.

The hydroxyl free radical, OH, is one of the most important radicals in atmospheric and interstellar chemistry, and its cation plays a role in the reactions leading to H2O formation. Knowledge of the photoionization efficiency of the OH radical is crucial to properly model the water photochemical cycle of atmospheres and astrophysical objects. Using a gas-phase radical source based on a single H-abstraction reaction combined with a photoelectron/photoion imaging coincidence spectrometer coupled with synchrotron radiation, we recorded the OH+ photoion yield over the 12.6-15 eV energy range, and we set it to an absolute cross section scale using an absolute point measurement performed at 13.8 eV: σOH ion=9.0±2.7 Mb. The resulting cross section values differ by approximately a factor 2 from the recent measurement of Dodson et al. [J. Chem. Phys. 148, 184302 (2018)] performed with a different radical source, which is somewhat greater than the combined uncertainties of the measurements. This finding underlines the need for further investigations of this cross section.

Valence-Shell Photoionization of C4H5: The 2-Butyn-1-yl Radical.

We present new high-resolution data on the photoionization of the 2-butyn-1-yl radical (CH3C≡C-•CH2) formed by H atom abstraction from 2-butyne by F atoms. The spectra were recorded from 7.7 to 11 eV by using double-imaging, photoelectron-photoion coincidence spectroscopy, which allows the unambiguous correlation of photoelectron data and the mass of the species. The photoionization spectrum shows significant resonant autoionizing structure converging to excited states of the C4H5+ cation, similar to what is observed in the closely related propargyl radical (HC≡C-•CH2). The threshold photoelectron spectrum, obtained with a resolution of 17 meV, is also reported. This spectrum is consistent with previous measurements of the first photoionization band but has been extended to higher energy to allow the observation of bands corresponding to excited electronic states of the ion. A refined value of the adiabatic ionization energy is extracted: IE(C4H5) = 7.93 ± 0.01 eV. A determination of the absolute photoionization cross section of the 2-butyn-1-yl radical at 9.7 eV is also reported: σion(C4H5) = 6.1 ± 1.8 Mb.