Abstract
Scanning tunneling spectroscopy (STS) is able to image a single molecule decoupled from its supporting substrate. The obtained images are routinely interpreted as the square moduli of molecular orbitals, dressed by the mean-field electron–electron interactions. Here, we demonstrate that the effect of electron correlation beyond the mean field qualitatively alters the uncorrelated STS images. After developing the proper many-body theoretical framework, we present the coupled-cluster calculation of the STS images of a planar molecule with a metal center, copper-(deh-salen). We find that many-body correlations alter significantly the image spectral weight close to the copper ion. This change is large enough to be assessed experimentally and survives to molecule–substrate interactions.
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Acknowledgments
Funding from INFM under the Young Researcher Seed Project 2008 initiative and Fondazione Cassa di Risparmio di Modena under the project COLDandFEW is gratefully acknowledged. Computer time has been provided by CINECA under the CINECA-ISCRA supercomputer project grants IscrB_FERMIFEW, IscrC_FEW1D, and IscrC_QUASIPAR.
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Rontani, M., Toroz, D., Corni, S. (2013). Visualizing Electron Correlation in Molecules Using a Scanning Tunneling Microscope: Theory and Ab Initio Prediction. 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_13
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DOI: https://doi.org/10.1007/978-3-642-38809-5_13
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