13 research outputs found
Electronic Properties of Vinylene-Linked Heterocyclic Conducting Polymers: Predictive Design and Rational Guidance from DFT Calculations
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
insure a low band gap. Rather, an iterative approach which destabilizes the
ground state of the parent polymer towards the aromatic \leftrightarrow
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.Comment: Accepted by the Journal of Physical Chemistry
Electronic Properties of Vinylene-Linked Heterocyclic Conducting Polymers: Predictive Design and Rational Guidance from DFT Calculations
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 <i>does not</i> ensure a low band gap. Rather, an iterative approach which destabilizes the ground state of the parent polymer toward the aromatic â 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