TY - JOUR
T1 - Optical absorptions in poly(paraphenylene vinylene) and poly(2,5-dimethoxy-1,4-paraphenylene vinylene) oligomers
AU - Cornil, J.
AU - Beljonne, D.
AU - Friend, R. H.
AU - Brédas, J. L.
N1 - 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).
PY - 1994/6/10
Y1 - 1994/6/10
N2 - 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).
AB - 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).
UR - http://www.scopus.com/inward/record.url?scp=0001884875&partnerID=8YFLogxK
U2 - 10.1016/0009-2614(94)00410-2
DO - 10.1016/0009-2614(94)00410-2
M3 - Article
AN - SCOPUS:0001884875
SN - 0009-2614
VL - 223
SP - 82
EP - 88
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 1-2
ER -
