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Theoretical investigation of molecular excited states in polar organic monolayers via an efficient embedding approach

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Abstract

In this work, we present a theoretical investigation on excitation energies of organic molecules embedded in a periodic monolayer. We use the self-consistent periodic-image-charges embedding approach, which takes into account all the electrostatic effects, to compute the perturbation on molecular orbitals and eigenvalues due to the presence of the surrounding periodic array of polar molecules. We considered vanadyl naphthalocyanine, mercaptobiphenyl, and tris-(8-hydroxyquinoline) aluminum (AlQ3) at different coverages, and excitation energies computed using the time-dependent density-functional theory. We found a significant (0.1–0.2 eV) red- or blue-shift of the energies for different excited states, due to the different coupling of the molecule with the polarization field of the two-dimensional crystal.

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Acknowledgments

We thank TURBOMOLE GmbH for providing us with the TURBOMOLE program package, and M. Margarito for technical support. This work was funded by the European Research Council (ERC) Starting Grant FP7 Project DEDOM, Grant Agreement No. 207441.

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Authors and Affiliations

  1. National Nanotechnology Laboratory (NNL), Istituto Nanoscienze-CNR, Via per Arnesano 16, 73100, Lecce, Italy

    Aleksandrs Terentjevs, Eduardo Fabiano & Fabio Della Sala

  2. Center for Biomolecular Nanotechnologies @UNILE, Istituto Italiano di Tecnologia (IIT), Via Barsanti, 73010, Arnesano, Italy

    Fabio Della Sala

Authors
  1. Aleksandrs Terentjevs
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  2. Eduardo Fabiano
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  3. Fabio Della Sala
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Correspondence to Fabio Della Sala.

Additional information

Dedicated to Professor Vincenzo Barone and published as part of the special collection of articles celebrating his 60th birthday.

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Terentjevs, A., Fabiano, E. & Della Sala, F. Theoretical investigation of molecular excited states in polar organic monolayers via an efficient embedding approach. Theor Chem Acc 131, 1154 (2012). https://doi.org/10.1007/s00214-012-1154-6

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