Solvation of O2- and O4- by p -difluorobenzene and p -xylene studied by photoelectron spectroscopy

Cheolhwa Kang, Jenny L. Troyer, Erika M. Robertson, David W. Rothgeb, Ekram Hossain, Richard B. Wyrwas, Charles S. Parmenter, Caroline Chick Jarrold

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Anion photoelectron spectra of the O2- arene and O4- arene complexes with p -xylene and p -difluorobenzene are presented and analyzed with the aid of calculations on the anions and corresponding neutrals. Relative to the adiabatic electron affinity of O2, the O2- arene spectra are blueshifted by 0.75-1 eV. Solvation energy alone does not account for this shift, and it is proposed that a repulsive portion of the neutral potential energy surface is accessed in the detachment, resulting in dissociative photodetachment. O2- is found to interact more strongly with the p -difluorobenzene than the p -xylene. The binding motif involves the O2- in plane with the arene, interacting via electron donation along nearby C-H bonds. A peak found at 4.36 (2) eV in the photoelectron spectrum of O2- p -difluorobenzene (p -DFB) is tentatively attributed to the charge transfer state, O2- p- DFB+. Spectra of O4- arene complexes show less blueshift in electron binding energy relative to the spectrum of bare O4-, which itself undergoes dissociative photodetachment. The striking similarity between the profiles of the O4- arene complexes with the O4- spectrum suggests that the O4- molecule remains intact upon complex formation, and delocalization of the charge across the O4- molecule results in similar structures for the anion and neutral complexes.

Original languageEnglish (US)
Article number104309
JournalJournal of Chemical Physics
Volume128
Issue number10
DOIs
StatePublished - 2008
Externally publishedYes

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Solvation
xylene
Photoelectron spectroscopy
Anions
solvation
photoelectron spectroscopy
Photoelectrons
Electron affinity
Potential energy surfaces
Molecules
photodetachment
Electrons
anions
Binding energy
Charge transfer
photoelectrons
electron affinity
detachment
4-xylene
molecules

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Kang, C., Troyer, J. L., Robertson, E. M., Rothgeb, D. W., Hossain, E., Wyrwas, R. B., ... Jarrold, C. C. (2008). Solvation of O2- and O4- by p -difluorobenzene and p -xylene studied by photoelectron spectroscopy. Journal of Chemical Physics, 128(10), [104309]. https://doi.org/10.1063/1.2838849

Solvation of O2- and O4- by p -difluorobenzene and p -xylene studied by photoelectron spectroscopy. / Kang, Cheolhwa; Troyer, Jenny L.; Robertson, Erika M.; Rothgeb, David W.; Hossain, Ekram; Wyrwas, Richard B.; Parmenter, Charles S.; Jarrold, Caroline Chick.

In: Journal of Chemical Physics, Vol. 128, No. 10, 104309, 2008.

Research output: Contribution to journalArticle

Kang, C, Troyer, JL, Robertson, EM, Rothgeb, DW, Hossain, E, Wyrwas, RB, Parmenter, CS & Jarrold, CC 2008, 'Solvation of O2- and O4- by p -difluorobenzene and p -xylene studied by photoelectron spectroscopy', Journal of Chemical Physics, vol. 128, no. 10, 104309. https://doi.org/10.1063/1.2838849
Kang, Cheolhwa ; Troyer, Jenny L. ; Robertson, Erika M. ; Rothgeb, David W. ; Hossain, Ekram ; Wyrwas, Richard B. ; Parmenter, Charles S. ; Jarrold, Caroline Chick. / Solvation of O2- and O4- by p -difluorobenzene and p -xylene studied by photoelectron spectroscopy. In: Journal of Chemical Physics. 2008 ; Vol. 128, No. 10.
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