Superatom spectroscopy and the electronic state correlation between elements and isoelectronic molecular counterparts

Edited by R. Stephen Berry, The University of Chicago, Chicago, Illinois, and approved December 2, 2009 (received for review October 5, 2009)
December 28, 2009
107 (3) 975-980

Abstract

Detailed in the present investigation are results pertaining to the photoelectron spectroscopy of negatively charged atomic ions and their isoelectronic molecular counterparts. Experiments utilizing the photoelectron imaging technique are performed on the negative ions of the group 10 noble metal block (i.e. Ni-, Pd-, and Pt-) of the periodic table at a photon energy of 2.33 eV (532 nm). The accessible electronic transitions, term energies, and orbital angular momentum components of the bound electronic states in the atom are then compared with photoelectron images collected for isoelectronic early transition metal heterogeneous diatomic molecules, M-X- (M = Ti,Zr,W; X = O or C). A superposition principle connecting the spectroscopy between the atomic and molecular species is observed, wherein the electronic structure of the diatomic is observed to mimic that present in the isoelectronic atom. The molecular ions studied in this work, TiO-, ZrO-, and WC- can then be interpreted as possessing superatomic electronic structures reminiscent of the isoelectronic elements appearing on the periodic table, thereby quantifying the superatom concept.

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Acknowledgments.

The authors thank G.J. Rathbone and W.C. Lineberger for stimulating conversations regarding photoelectron imaging. We gratefully acknowledge funding from the Air Force Office of Scientific Research Grant FA 9550-07-1-0151.

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Published in

The cover image for PNAS Vol.107; No.3
Proceedings of the National Academy of Sciences
Vol. 107 | No. 3
January 19, 2010
PubMed: 20080555

Classifications

Submission history

Published online: December 28, 2009
Published in issue: January 19, 2010

Keywords

  1. cluster anions
  2. photoelectron imaging
  3. superatoms
  4. angular distributions
  5. transition metal

Acknowledgments

The authors thank G.J. Rathbone and W.C. Lineberger for stimulating conversations regarding photoelectron imaging. We gratefully acknowledge funding from the Air Force Office of Scientific Research Grant FA 9550-07-1-0151.

Notes

This article is a PNAS Direct Submission.

Authors

Affiliations

Samuel J. Peppernick
Department of Materials Science and Engineering,
K.D. Dasitha Gunaratne
Department of Chemistry, and
A.W. Castleman, Jr.1 [email protected]
Department of Chemistry, and
Department of Physics, 104 Chemistry Research Building, Pennsylvania State University, University Park, PA 16802.

Notes

1
To whom correspondence should be addressed. E-mail: [email protected].
Author contributions: S.J.P., K.D.D.G., and A.W.C. designed research, performed research, analyzed data, and wrote the paper.

Competing Interests

The authors declare no conflict of interest.

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    Superatom spectroscopy and the electronic state correlation between elements and isoelectronic molecular counterparts
    Proceedings of the National Academy of Sciences
    • Vol. 107
    • No. 3
    • pp. 949-1254

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