Electronic and optical properties of hexathiapentacene in the gas and crystal phases

R. Cardia, G. Malloci, G.-M. Rignanese, X. Blase, E. Molteni, and G. Cappellini
Phys. Rev. B 93, 235132 – Published 16 June 2016
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Abstract

Using density functional theory (DFT) and its time-dependent (TD) extension, the electronic and optical properties of the hexathiapentacene (HTP) molecule, a derivative of pentacene (PNT) obtained by symmetric substitution of the six central H atoms with S atoms, are investigated for its gas and solid phases. For the molecular structure, all-electron calculations are performed using a Gaussian localized orbital basis set in conjunction with the Becke three-parameter Lee-Yang-Parr (B3LYP) hybrid exchange-correlation functional. Electron affinities, ionization energies, quasiparticle energy gaps, optical absorption spectra, and exciton binding energies are calculated and compared with the corresponding results for PNT, as well as with the available experimental data. The DFT and TDDFT results are also validated by performing many-body perturbation theory calculations within the GW and Bethe-Salpeter equation formalisms. The functionalization with S atoms induces an increase of both ionization energies and electron affinities, a sizable reduction of the fundamental electronic gap, and a redshift of the optical absorption onset. Notably, the intensity of the first absorption peak of HTP falling in the visible region is found to be nearly tripled with respect to the pure PNT molecule. For the crystal structures, pseudopotential calculations are adopted using a plane-wave basis set together with the Perdew-Burke-Ernzerhof exchange-correlation functional empirically corrected in order to take dispersive interactions into account. The electronic excitations are also obtained within a perturbative B3LYP scheme. A comparative analysis is carried out between the ground-state and excited-state properties of crystalline HTP and PNT linking to the findings obtained for the isolated molecules.

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  • Received 25 November 2015
  • Revised 27 May 2016

DOI:https://doi.org/10.1103/PhysRevB.93.235132

©2016 American Physical Society

Authors & Affiliations

R. Cardia1,2, G. Malloci1,*, G.-M. Rignanese3, X. Blase4, E. Molteni5, and G. Cappellini1,2,†

  • 1Università degli Studi di Cagliari, Dipartimento di Fisica, Cittadella Universitaria, I-09042 Monserrato (Cagliari), Italy
  • 2Istituto Officina dei Materiali (CNR-IOM), UOS di Cagliari, Cittadella Universitaria, I-09042 Monserrato (Cagliari), Italy
  • 3Institute of Condensed Matter and Nanoscience (IMCN), Université Catholique de Louvain, B-1348 Louvain-la-neuve, Belgium
  • 4CNRS and Grenoble-Alpes University, Institut Néel, F-38042 Grenoble, France
  • 5Università degli Studi di Milano, Dipartimento di Fisica, Milano, Italy

  • *giuliano.malloci@dsf.unica.it
  • giancarlo.cappellini@dsf.unica.it

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Vol. 93, Iss. 23 — 15 June 2016

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