NEGATIVE ION PHOTOELECTRON SPECTROSCOPY OF: $NO^{-}(Ar)_{1}, NO^{-}(Kr)_{1}, NO^{-}(Xe)_{1}$, AND $N_{2}O_{2}$

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1987

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Ohio State University

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We have recorded the photoelectrom (photodetachment) spectra of the gasphase negative ions: NO(Ar)1,NO(Kr)1, and NO−(Xe)1 using 2.409 eV photons, and of N2O2 using both 2.540 eV and 2.707 eV photons. All of these ions were generated in a supersonic expansion ion source with various mixtures of nitric oxide and rare gases. All of the rare gas negative cluster ion spectra exhibit structured spectral patterns which strongly resemble that obtained for free NO, but which are shifted to lower electron energies with their individual peaks broadened. Each of these spectra is interpreted in terms of a largely intact NO sub-ion which is solvated and stabilized by its rare gas solvent atom. The ion-solvent dissociation energy for a given NO−(Rg)1 cluster ion dissociating into NO and Rg is given by the energy difference between the origin peak of the free NO spectrum and the origin peak of a given NO(Rg)1 spectrum. The values of these shifts were found to be: 0.058±0.011eV,0.099±0.018eV,0.161±0.024eV for the argon, krypton, and xenon complexes, respectively. Values for the electron affinities of these complexes were found to be: 0.095 eV, 0.136 eV, and 0.204 eV for the argon, krypton, and xenon complexes, respectively. Both of our photoelectron spectra for N2O2 came at the low electron energy end of our spectral range. The electron affinity of the N2O2 species studied here can be given a lower bound of 2.1 eV. Studies by Johnson1 at higher photon energies indicate the existence of other isomers as well.

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1 M. A. Johnson (private communication)


Author Institution: Westinghouse R & D Center; Dept. of Chemistry, The Johns Hopkins University

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