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Imaging Orbitals by Ionization or Electron Attachment: The Role of Dyson Orbitals

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Imaging and Manipulating Molecular Orbitals

Part of the book series: Advances in Atom and Single Molecule Machines ((AASMM))

Abstract

Molecular orbitals are one-electron wave functions computed at a mean field level of approximation in electronic structure theory. Spatially resolved scanning tunneling microscopy (STM) experiments probe the electron density of a species with an extra electron or with a default of one electron, which strictly speaking, corresponds to a Dyson orbital. Dyson orbitals are one-electron wave functions that represent the density of the electron that is removed or attached to the molecule. They provide a correlated view of the wave function of the leaving electron. They are computed as the overlap between the neutral species and the species with a defect of one electron or an extra one. Dyson orbitals correspond to molecular orbitals of the neutral only when there is little electron relaxation in the charged species with respect to the neutral. They also play a crucial role in the interpretation of photoelectron angular distributions. We discuss the properties of Dyson orbitals in pentacene for electron attachment and removal and in C60 and LiH with special reference to photoelectron angular distributions and the probing of ultrafast electron dynamics.

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Acknowledgments

We thank C. Joachim and W. H. Soe for stimulating discussions on the pentacene molecule at the occasion of the ATMOL conference in Berlin. We gratefully acknowledge support from the Fonds de la Recherche Fondamentale Collective FRFC 2.4545.12 ‘Control of attosecond dynamics’. FR is a Director of Research and BM is a PhD fellow of Fonds National de la Recherche Scientifique (FNRS, Belgium). TK acknowledges FNRS for a post-doctoral fellowship (FRFC 2.4545.12).

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Authors and Affiliations

  1. Department of Chemistry, B6c, University of Liège, B4000, Liège, Belgium

    B. Mignolet, T. Kùs & F. Remacle

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  1. B. Mignolet
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  2. T. Kùs
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  3. F. Remacle
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Correspondence to F. Remacle .

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Editors and Affiliations

  1. Fritz-Haber-Institute Department of Physical Chemistry, Berlin, Germany

    Leonhard Grill

  2. GNS, CNRS, Toulousse Cedex, France

    Christian Joachim

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Mignolet, B., Kùs, T., Remacle, F. (2013). Imaging Orbitals by Ionization or Electron Attachment: The Role of Dyson Orbitals. In: Grill, L., Joachim, C. (eds) Imaging and Manipulating Molecular Orbitals. Advances in Atom and Single Molecule Machines. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-38809-5_4

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