Accurate prediction of band gaps in neutral heterocyclic conjugated polymers

Geoffrey R. Hutchison, Mark A Ratner, Tobin J Marks

Research output: Contribution to journalArticle

128 Citations (Scopus)

Abstract

Heterocyclic π-electron polymers such as polythiophene, polypyrrole, and polyfuran attract wide interest on both experimental and theoretical levels. While the optical properties of these materials are dominated by the band gap, no accurate, reliable computational method currently exists to predict the band gaps of large oligomers. Six computational methods, including ZINDO/CIS, ZINDO/RPA, HF/CIS, HF/RPA, TDDFT/ TDA, and TDDFT are compared here for a set of 60 structurally well-defined heterocyclic oligomers of varied structure. All six methods are compared using both AM1 semiempirical and B3LYP DFT predicted geometries. Among the methods, the semiempirical ZINDO/CIS method applied to DFT-predicted geometries affords the best agreement between computed and experimental band gaps, yielding an RMS error of 0.31 eV over the data set considered. Analysis of the computed band gaps provides a simple, straightforward empirical correction that significantly improves the accuracy of all six methods, with RMS errors between 0.23 eV and 0.44 eV for TDDFT using DFT-predicted geometries and for ZINDO/RPA using AM1-predicted geometries, respectively.

Original languageEnglish
Pages (from-to)10596-10605
Number of pages10
JournalJournal of Physical Chemistry A
Volume106
Issue number44
DOIs
Publication statusPublished - Nov 7 2002

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Conjugated polymers
Commonwealth of Independent States
Energy gap
Discrete Fourier transforms
Geometry
polymers
Computational methods
geometry
predictions
oligomers
Oligomers
polypyrroles
Polymers
Optical properties
optical properties
Electrons
electrons

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Accurate prediction of band gaps in neutral heterocyclic conjugated polymers. / Hutchison, Geoffrey R.; Ratner, Mark A; Marks, Tobin J.

In: Journal of Physical Chemistry A, Vol. 106, No. 44, 07.11.2002, p. 10596-10605.

Research output: Contribution to journalArticle

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