Spontaneous Charge Carrier Localization in Extended One-Dimensional Systems

Vojtěch Vlček, Helen R. Eisenberg, Gerd Steinle-Neumann, Daniel Neuhauser, Eran Rabani, and Roi Baer
Phys. Rev. Lett. 116, 186401 – Published 2 May 2016
PDFHTMLExport Citation

Abstract

Charge carrier localization in extended atomic systems has been described previously as being driven by disorder, point defects, or distortions of the ionic lattice. Here we show for the first time by means of first-principles computations that charge carriers can spontaneously localize due to a purely electronic effect in otherwise perfectly ordered structures. Optimally tuned range-separated density functional theory and many-body perturbation calculations within the GW approximation reveal that in trans-polyacetylene and polythiophene the hole density localizes on a length scale of several nanometers. This is due to exchange-induced translational symmetry breaking of the charge density. Ionization potentials, optical absorption peaks, excitonic binding energies, and the optimally tuned range parameter itself all become independent of polymer length as it exceeds the critical localization length. Moreover, we find that lattice disorder and the formation of a polaron result from the charge localization in contrast to the traditional view that lattice distortions precede charge localization. Our results can explain experimental findings that polarons in conjugated polymers form instantaneously after exposure to ultrafast light pulses.

  • Figure
  • Figure
  • Figure
  • Figure
  • Received 21 September 2015

DOI:https://doi.org/10.1103/PhysRevLett.116.186401

© 2016 American Physical Society

Physics Subject Headings (PhySH)

Condensed Matter, Materials & Applied PhysicsPolymers & Soft Matter

Authors & Affiliations

Vojtěch Vlček1,2, Helen R. Eisenberg1, Gerd Steinle-Neumann2, Daniel Neuhauser3, Eran Rabani4,5, and Roi Baer1

  • 1Fritz Haber Center for Molecular Dynamics, Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel
  • 2Bayerisches Geoinstitut, Universität Bayreuth, Bayreuth 95440, Germany
  • 3Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA
  • 4Department of Chemistry, University of California and Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
  • 5The Sackler Center for Computational Molecular and Materials Science, Tel Aviv University, Tel Aviv 69978, Israel

Article Text (Subscription Required)

Click to Expand

Supplemental Material (Subscription Required)

Click to Expand

References (Subscription Required)

Click to Expand
Issue

Vol. 116, Iss. 18 — 6 May 2016

Reuse & Permissions
Access Options
CHORUS

Article Available via CHORUS

Download Accepted Manuscript

Authorization Required


×
×

Images

×

Sign up to receive regular email alerts from Physical Review Letters

Log In

Cancel
×

Search


Article Lookup

Paste a citation or DOI

Enter a citation
×