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

Hrodmarsson, H. R.; Loison, J. -C.; Jacovella, U.; Holland, D. M.  P.; Boyé-Péronne, S.; Gans, B.; Garcia, G. A.; Nahon, L.; Pratt, S. T.

doi:10.1021/acs.jpca.8b11809

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

Journal Article · Mon Jan 28 23:00:00 EST 2019 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.8b11809· OSTI ID:1509986

Hrodmarsson, H. R. ^[1]; Loison, J. -C. ^[2]; Jacovella, U. ^[3]; Holland, D. M. P. ^[4]; Boyé-Péronne, S. ^[5]; ^[5]; ^[1]; Nahon, L. ^[1]; ^[6]

Synchrotron Soleil, Gif-sur-Yvette (France)
Univ. of Bordeaux (France). Inst. of Molecular Sciences
Swiss Federal Inst. of Technology in Zurich (ETH Zurich) (Switzerland). Lab. of Physical Chemistry
Science and Technology Facilities Council (STFC), Daresbury (United Kingdom). Daresbury Lab.
Univ. Paris-Sud, Orsay (France). Inst. of Molecular Sciences of Orsay (ISMO)
Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division

We present here 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: σ_ion(C₄H₅) = 6.1 ± 1.8 Mb.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States); Science and Technology Facilities Council (STFC), Daresbury (United Kingdom); Synchrotron Soleil, Gif-sur-Yvette (France); Univ. Paris-Sud, Orsay (France)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Science and Technology Facilities Council (STFC) (United Kingdom); National Research Agency (ANR) (France)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1509986

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 8 Vol. 123; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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