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Negative electron binding energies observed in a triply charged anion: Photoelectron spectroscopy of 1-hydroxy-3,6,8-pyrene-trisulfonate

J. Chem. Phys. 128, 091102 (2008); doi:10.1063/1.2889001

Published 4 March 2008

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Jie Yang,1,2 Xiao-Peng Xing,1,2 Xue-Bin Wang,1,2 Lai-Sheng Wang,1,2 Alina P. Sergeeva,3 and Alexander I. Boldyrev3
1Department of Physics, Washington State University, 2710 University Drive, Richland, Washington 99354, USA
2Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, MS K8-88, P.O. Box 999, Richland, Washington 99352, USA
3Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322, USA
We report the observation of negative electron binding energies (BEs) in a triply charged anion, 1-hydroxy-3,6,8-pyrene-trisulfonate (HPTS3−). Low-temperature photoelectron spectra were obtained for HPTS3− at several photon energies, revealing three detachment features below 0 electron BE. The HPTS3− trianion was measured to possess a negative BE of −0.66  eV. Despite the relatively high excess energy stored in HPTS3−, it was observed to be a long-lived anion due to its high repulsive Coulomb barrier (RCB) (~3.3  eV), which prevents spontaneous electron emission. Theoretical calculations were carried out, which confirmed the negative electron BEs observed. The calculations further showed that the highest occupied molecular orbital in HPTS3− is an antibonding pi orbital on the pyrene rings, followed by lone pair electrons in the peripheral –SO3− groups. Negative electron BE is a unique feature of multiply charged anions due to the presence of the RCB. Such metastable species may be good models to study electron-electron and vibronic interactions in complex molecules. ©2008 American Institute of Physics
History: Received 16 January 2008; accepted 6 February 2008; published 4 March 2008
Permalink: http://link.aip.org/link/?JCPSA6/128/091102/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.15.Ry
    Molecular ionization potentials, electron affinities, molecular core binding energy
  • 33.60.+q
    Photoelectron spectra of molecules
  • 33.20.Wr
    Vibronic, rovibronic, and rotation-electron-spin interactions (molecular spectra)
  • 33.80.Eh
    Autoionization, photoionization, and photodetachment of molecules
  • 31.15.V-
    Electron correlation calculations for atoms, ions and molecules
  • YEAR: 2008

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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