Solvation of O{sub 2}{sup -} and O{sub 4}{sup -} by p-difluorobenzene and p-xylene studied by photoelectron spectroscopy
- Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405 (United States)
Anion photoelectron spectra of the O{sub 2}{sup -}{center_dot}arene and O{sub 4}{sup -}{center_dot}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 O{sub 2}, the O{sub 2}{sup -}{center_dot}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. O{sub 2}{sup -} is found to interact more strongly with the p-difluorobenzene than the p-xylene. The binding motif involves the O{sub 2}{sup -} 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 O{sub 2}{sup -}{center_dot}p-difluorobenzene (p-DFB) is tentatively attributed to the charge transfer state, O{sub 2}{sup -}{center_dot}p-DFB{sup +}. Spectra of O{sub 4}{sup -}{center_dot}arene complexes show less blueshift in electron binding energy relative to the spectrum of bare O{sub 4}{sup -}, which itself undergoes dissociative photodetachment. The striking similarity between the profiles of the O{sub 4}{sup -}{center_dot}arene complexes with the O{sub 4}{sup -} spectrum suggests that the O{sub 4}{sup -} molecule remains intact upon complex formation, and delocalization of the charge across the O{sub 4}{sup -} molecule results in similar structures for the anion and neutral complexes.
- OSTI ID:
- 21104001
- Journal Information:
- Journal of Chemical Physics, Vol. 128, Issue 10; Other Information: DOI: 10.1063/1.2838849; (c) 2008 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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