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

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4 Scopus citations

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 - Mar 25 2008

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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    Kang, C., Troyer, J. L., Robertson, E. M., Rothgeb, D. W., Hossain, E., Wyrwas, R. B., Parmenter, C. S., & 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