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Journal of Chemical Physics / Volume 133 / Issue 13 / ARTICLES / Gas Phase Dynamics and Structure: Spectroscopy, Molecular Interactions, Scattering, and Photochemistry

J. Chem. Phys. 133, 134302 (2010); http://dx.doi.org/10.1063/1.3488103 (7 pages)

The applicability of three-dimensional aromaticity in BiSnn− Zintl analogues

Peneé A. Clayborne1,2, Ujjwal Gupta3, Arthur C. Reber1, Joshua J. Melko3, Shiv N. Khanna1, and A. W. Castleman, Jr.3

1Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284, USA
2Department of Chemistry, Nanoscience Center, University of Jyväskylä, Jyväskylä FI-40014, Finland
3Department of Chemistry and Department of Physics, The Pennsylvania State University, University Park, Pennsylvania 16802, USA

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(Received 7 July 2010; accepted 18 August 2010; published online 1 October 2010)

Three-dimensional aromaticity is shown to play a role in the stability of deltahedral Zintl clusters and here we examine the connection between aromaticity and stability. In order to gain further insight, we have studied Zintl analogs comprised of bismuth doped tin clusters with photoelectron spectroscopy and theoretical methods. To assign aromaticity, we examine the ring currents induced around the cage by using the nucleus independent chemical shift. In the current study, BiSn4− is a stable cluster and fits aromatic criteria, while BiSn5− is found to fit antiaromatic criteria and has reduced stability. The more stable clusters exhibit an aromatic character which originates from weakly interacting s-states and bonding orbitals parallel to the surface of the cluster, while nonbonding lone pairs perpendicular to the surface of the cluster account for antiaromaticity and reduced stability. The effect of three-dimensional aromaticity on the electronic structure does not result in degeneracies, so the resulting variations in stability are smaller than those seen in conventional aromaticity.

© 2010 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. EXPERIMENTAL METHOD
  3. THEORETICAL METHOD
  4. RESULTS
  5. CONCLUSIONS

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KEYWORDS and PACS

Keywords

bismuth compounds, chemical shift, doping profiles, molecular clusters, photoelectron spectra, tin

PACS

  • 36.40.Qv

    Stability and fragmentation of clusters

  • 33.60.+q

    Photoelectron spectra

  • 36.40.Wa

    Charged clusters

  • 36.40.Mr

    Spectroscopy and geometrical structure of clusters

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3488103

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.
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