Nature of charge carriers in long doped oligothiophenes: The effect of counterions

Natalia Zamoshchik, Ulrike Salzner, Michael Bendikov

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

A series of oligothiophene dications doped with Cl3 - ions were studied using density functional theory (DFT) at the B3LYP/6-31G(d) level. The balance between the bipolaron and polaron pair states was addressed by studying the closed-shell singlet, open-shell singlet, and triplet states of oligothiophene divalent salts using the relative energies of the different isomers, differences between the singlet and triplet states, bond length alternation analysis, charge distribution analysis, and isodesmic reactions. We found that contribution of polaron pair state to the electronic structure of the oligothiophene divalent salts is not observed in 8T2+(Cl3́ -)2 (short oligothiophene salts), appears in 12T 2+(Cl3 -)2 (medium-sized oligothiophene salts), and becomes the dominant in 20T2+(Cl 3 -)2 (long oligothiophene salts). Bipolarons are intrinsically unstable with respect to dissociation into polaron pairs regardless of the presence of counterions. Thus, even in the presence of counterions, we did not observe any bipolaron stabilization energy, however, doping ions localize polarons. The singlet and triplet states are energetically degenerate for long oligothiophene divalent salts, such as 20T 2+(Cl3 -)2.

Original languageEnglish
Pages (from-to)8408-8418
Number of pages11
JournalJournal of Physical Chemistry C
Volume112
Issue number22
DOIs
Publication statusPublished - Jun 5 2008

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Charge carriers
charge carriers
Salts
salts
Gene Conversion
atomic energy levels
Ions
Polarons
Charge distribution
alternations
Bond length
polarons
Isomers
charge distribution
Electronic structure
Density functional theory
ions
isomers
Stabilization
stabilization

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Nature of charge carriers in long doped oligothiophenes : The effect of counterions. / Zamoshchik, Natalia; Salzner, Ulrike; Bendikov, Michael.

In: Journal of Physical Chemistry C, Vol. 112, No. 22, 05.06.2008, p. 8408-8418.

Research output: Contribution to journalArticle

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