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Electronic Properties of Vinylene-Linked Heterocyclic Conducting Polymers: Predictive Design and Rational Guidance from DFT Calculations

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Bryan M. Wong* and Joseph G. Cordaro

Materials Chemistry Department, Sandia National Laboratories, Livermore, California 94551, United States

J. Phys. Chem. C, 2011, 115 (37), pp 18333–18341

DOI: 10.1021/jp204849e

Publication Date (Web): July 13, 2011

E-mail: bmwong@sandia.gov. Web: http://alum.mit.edu/www/usagi.

Section:

Physical Properties of Synthetic High Polymers

Abstract

The band structure and electronic properties in a series of vinylene-linked heterocyclic conducting polymers are investigated using density functional theory (DFT). In order to accurately calculate electronic band gaps, we utilize hybrid functionals with fully periodic boundary conditions to understand the effect of chemical functionalization on the electronic structure of these materials. The use of predictive first-principles calculations coupled with simple chemical arguments highlights the critical role that aromaticity plays in obtaining a low band gap polymer. Contrary to some approaches which erroneously attempt to lower the band gap by increasing the aromaticity of the polymer backbone, we show that being aromatic (or quinoidal) in itself does not ensure a low band gap. Rather, an iterative approach which destabilizes the ground state of the parent polymer toward the aromatic ↔ quinoidal level crossing on the potential energy surface is a more effective way of lowering the band gap in these conjugated systems. Our results highlight the use of predictive calculations guided by rational chemical intuition for designing low band gap polymers in photovoltaic materials.

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This article has been cited by 1 ACS Journal articles (1 most recent appear below).

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- Anomalous Optoelectronic Properties of Chiral Carbon Nanorings…and One Ring to Rule Them All(23)
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  The Journal of Physical Chemistry Letters2011 2 (21), 2702-2706
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