Abstract
On the basis of geometries optimized at the Austin model 1 level, we use the intermediate neglect of differential overlap method coupled with a single configuration interaction technique to calculate the optical absorption spectra of oligomers of poly(paraphenylene vinylene), PPV, and their dimethoxy-substituted derivatives. Our results are in good agreement with experimentally measured visible and UV absorption spectra for oligomers and polymers, and provide a detailed interpretation of the electronic transitions involved, distinguishing the roles of localized and delocalized π molecular orbitals. In addition to the lowest energy transition, from highest occupied to lowest unoccupied delocalized π orbitals (2.5 eV in PPV), we calculate further structure in the absorption at higher energies associated with the delocalized π orbitals. These match well the measured absorption features in PPV compounds, at 4.5 eV (tetramer), 4.1 eV (pentamer) and 3.8 eV (hexamer, polymer).
| Original language | English (US) |
|---|---|
| Pages (from-to) | 82-88 |
| Number of pages | 7 |
| Journal | Chemical Physics Letters |
| Volume | 223 |
| Issue number | 1-2 |
| DOIs | |
| State | Published - Jun 10 1994 |
| Externally published | Yes |
Bibliographical note
Funding Information:This work is partlys upportedb y the Commission of EuropeanC ommunityE SPRIT projectL EDFOS-8013,t he BelgianP rime Minister Office of Science Policy “Programmed ’Impulsione n Technologied e 1’Informationa” nd“ Pole d’Attractione nC himieS u-pramoleculaireet Catalyse”,F NRS/FRFC, and an IBM AcademicJo int Study.O ne of us (DB) thanks the “Institut pour 1’Encouragemednet la Recherche dansl ’Industriee t l’AgricuIture( IRSIA)” for financial support.A nothero f us (JC) is Aspiranto f the Belgian National Fund for Scientific Research (FNRS).
ASJC Scopus subject areas
- General Physics and Astronomy
- Physical and Theoretical Chemistry
