Influence of push-pull group substitution patterns on excited state properties of donor-acceptor co-monomers and their trimers

Hilde D. de Gier, Bernd J. Rietberg, Ria Broer*, Remco W. A. Havenith

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

5 Citations (Scopus)


Organic electronics form a very promising new generation of cheap, lightweight and flexible devices. Of special interest is the ability to engineer photo-physical properties of organic molecules by chemical modification. In this regard, the purpose of this research is to understand the influence of push-pull group substitution patterns on excited state properties of several donor-acceptor co-monomers an their trimers. Part of this work focuses on organic photovoltaic applications to demonstrate the practical use of the structure-property relations. In this context, the strong exciton binding energy determined by the electron-hole interaction is an important property. (Time-dependent) Density Functional Theory calculations showed a significant difference between linear- and cross-conjugated push-pull group pathways for the electron-hole interaction and the vertical exciton binding energy, which can be understood from simple Huckel theory. A linear relation between the dipole moment change upon excitation and the vertical exciton binding energy hints to a possible correlation, although this relation is less pronounced for the trimers. The overlap density between the frontier molecular orbitals alone already reveals valuable information about the relative size of the electron-hole interaction and the vertical exciton binding energy. Application of our findings in the context of organic photovoltaics results in significant support for cross-conjugated mesomeric push-pull group pathways in order to spatially separate the HOMO and LUMO. (C) 2014 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)202-211
Number of pages10
JournalComputational and Theoretical Chemistry
Publication statusPublished - 15-Jul-2014


  • Donor-acceptor co-monomers and trimers
  • Inductive and mesomeric push-pull groups
  • Linear- and cross-conjugation
  • Excited state properties
  • (Time-dependent) Density Functional Theory
  • Organic photovoltaics
  • GAP
  • CC2

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