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Study of N{sub 2}O{sub 2} by photoelectron spectroscopy of N{sub 2}O{sub 2}{sup {minus}}

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.469097· OSTI ID:45978
;  [1]
  1. Department of Chemistry, University of California, Berkeley, Berkeley, California 94720 (United States)
Photoelectron spectra of the N{sub 2}O{sup {minus}}{sub 2} anion, collected at {ital h}{nu}=4.657 and 5.822 eV, are presented. The spectra originate from the {ital C}{sub 2{ital v}} isomer of the anion. Vibrationally resolved progressions corresponding to transitions to several electronic states of the previously unobserved N{sub 2}O{sub 2} molecule are observed. All of the observed transitions lie above the dissociation asymptotes for N{sub 2}+O{sub 2}, NO+NO, and O+N{sub 2}O, and several lie above the N+NO{sub 2} and N{sub 2}+O+O asymptotes. {ital Ab} {ital initio} calculations have been carried out for the anion ground state and several singlet and triplet states of neutral N{sub 2}O{sub 2}. By comparing the observed spectra with Franck--Condon simulations based on these calculations, the lowest bands observed in our spectra were assigned to transitions to the {sup 3}{ital A}{sub 2} and {sup 3}{ital A}{sub 1} states ({ital C}{sub 2{ital v}} symmetry) of N{sub 2}O{sub 2}. These spectra thus represent the first experimental characterization of metastable, high energy forms of N{sub 2}O{sub 2}. Both the N{sub 2}O{sup {minus}}{sub 2} and the N{sub 2}O{sub 2} species are considered in terms of their roles as reactive intermediates in the O{sup {minus}}+N{sub 2}O and N+NO{sub 2} chemical reactions.
OSTI ID:
45978
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 18 Vol. 102; ISSN JCPSA6; ISSN 0021-9606
Country of Publication:
United States
Language:
English

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