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Journal of Chemical Physics / Volume 128 / Issue 9 / COMMUNICATIONS

J. Chem. Phys. 128, 091102 (2008); http://dx.doi.org/10.1063/1.2889001 (4 pages)

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

Jie Yang1,2, Xiao-Peng Xing1,2, Xue-Bin Wang1,2, Lai-Sheng Wang1,2, Alina P. Sergeeva3, 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

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(Received 16 January 2008; accepted 6 February 2008; published online 4 March 2008)

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 π 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

Article Outline

  1. INTRODUCTION
  2. EXPERIMENTAL AND THEORETICAL METHODS
    1. Photoelectron spectroscopy
    2. Theoretical calculations
  3. RESULTS AND DISCUSSION

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KEYWORDS and PACS

Keywords

binding energy, bonds (chemical), electron correlations, electron detachment, metastable states, negative ions, organic compounds, photoelectron spectra, vibronic states

PACS

  • 33.15.Ry

    Ionization potentials, electron affinities, molecular core binding energy

  • 33.60.+q

    Photoelectron spectra

  • 33.20.Wr

    Vibronic, rovibronic, and rotation-electron-spin interactions

  • 33.80.Eh

    Autoionization, photoionization, and photodetachment

  • 31.15.V-

    Electron correlation calculations for atoms, ions and molecules

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.2889001

PUBLICATION DATA

ISSN

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

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

For access to fully linked references, you need to log in.
    S. N. Schauer, P. Williams, and R. N. Compton, Phys. Rev. Lett. 65, 625 (1990).

    X. B. Wang, C. F. Ding, and L. S. Wang, Phys. Rev. Lett. 81, 3351 (1998).

    L. S. Wang, C. F. Ding, X. B. Wang, and J. B. Nicholas, Phys. Rev. Lett. 81, 2667 (1998).

    X. B. Wang and L. S. Wang, Phys. Rev. Lett. 83, 3402 (1999).

    M. N. Blom, O. Hampe, S. Gilb, P. Weis, and M. M. Kappes, J. Chem. Phys. 115, 3690 (2001)JCPSA6000115000008003690000001.

    D. B. Spry, A. Goun, C. B. Bell III, and M. D. Fayer, J. Chem. Phys. 125, 144514 (2006)JCPSA6000125000014144514000001.

    X. B. Wang, H. K. Woo, and L. S. Wang, J. Chem. Phys. 123, 051106 (2005)JCPSA6000123000005051106000001.

    A. D. Becke, J. Chem. Phys. 98, 5648 (1993)JCPSA6000098000007005648000001.

    C. Lee, W. Yang, and R. G. Parr, Phys. Rev. B 37, 785 (1988).

    T. H. Dunning, Jr., J. Chem. Phys. 90, 1007 (1989)JCPSA6000090000002001007000001.

    D. E. Woon and T. H. Dunning, Jr., J. Chem. Phys. 98, 1358 (1993)JCPSA6000098000002001358000001.


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