Abstract
The influence of chemical defects and conformational kinks on the nature of the lowest electronic excitations in phenylenevinylene-based polymers is assessed at the semiempirical quantum-chemical level. The amount of excited-state localization and the amplitude of through-space (Coulomb-like) versus through-bond (charge-transfer-like) interactions have been quantified by comparing the results provided by excitonic and supermolecular models. While excitation delocalization among conjugated segments delineated by the defects occurs in the acceptor configuration, self-confinement on individual chromophores follows from geometric relaxation in the excited-state donor configuration. The extent of excited-state localization is found to be sensitive to both the nature of the defect and the length of the conjugated chains. Implications for resonant energy transfer along conjugated polymer chains are discussed.
| Original language | English (US) |
|---|---|
| Article number | 054901 |
| Journal | JOURNAL OF CHEMICAL PHYSICS |
| Volume | 125 |
| Issue number | 5 |
| DOIs | |
| State | Published - 2006 |
| Externally published | Yes |
Bibliographical note
Funding Information:The authors gratefully acknowledge the Belgian National Fund for Scientific Research (FNRS-FRFC) for its financial support. E.H. and D.B. are FNRS Postdoctoral Research Fellow and Research Associate, respectively. C.D. acknowledges a grant from FRIA (“Fonds pour la Formation à la Recherche dans 1’Industrie et dans 1’Agriculture”). The work at Georgia Tech is partly supported by the Office of Naval Research and the National Science Foundation (through the STC program under Award No. DMR-0120967 and Grant No. CHE-0342321). G.D.S. thanks the Natural Sciences and Engineering Research Council, Canada and the Alfred P. Sloan Foundation.
ASJC Scopus subject areas
- General Physics and Astronomy
- Physical and Theoretical Chemistry