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    Band Formation in a Molecular Quantum Well via 2D Superatom Orbital Interactions

    Daniel B. Dougherty1,*, Min Feng2, Hrvoje Petek2,‡, John T. Yates, Jr.1,†, and Jin Zhao2,3,‡

    • 1Surface Science Center and Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA
    • 2Department of Physics and Astronomy, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA
    • 3Hefei National Laboratory for Physical Sciences at Microscale and Department of Physics, University of Science and Technology of China, Hefei, Anhui 230026, People’s Republic of China

    • *Present address: Department of Physics, North Carolina State University, Raleigh, NC 27695, USA.
    • †Present address: Department of Chemistry, University of Virginia, Charlottesville, VA 22904, USA.
    • ‡Corresponding authors. petek@pitt.edu zhaojin@ustc.edu.cn
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    Phys. Rev. Lett. 109, 266802 – Published 26 December, 2012

    DOI: https://doi.org/10.1103/PhysRevLett.109.266802

    Abstract

    By scanning tunneling microscopy and spectroscopy, we study nearly free electron band formation of the σ* lowest unoccupied molecular orbital of C6F6 on a Cu(111) surface. In fractal islands, the lowest unoccupied molecular orbital energy systematically stabilizes with the number of interacting near-neighbor C6F6 molecules. Density functional theory calculations reveal the origin of effective intermolecular orbital overlap in the previously unrecognized superatom character of the σ* orbital of C6F6 molecules. The discovery of superatom orbitals in planar molecules offers a new universal principle for effective band formation, which can be exploited in designing organic semiconductors with nearly free electron properties.

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    Phys. Rev. Lett. 109, 266802– Published 26 December, 2012
    • Received 11 May 2012

    © 2012 American Physical Society

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