On the nature of electronic excitations in poly(paraphenylenevinylene): A quantum-chemical investigation

D. Beljonne, Z. Shuai, J. Cornil, D. A. Dos Santos, J. L. Brédas

Research output: Contribution to journalArticlepeer-review

51 Scopus citations


Correlated quantum-chemical calculations are performed on phenylenevinylene oligomers containing up to eleven repeat units, to characterize the nature of the electronic excitations relevant for the photophysical properties of the corresponding polymer. The focus is first on the nonlinear optical response of model conjugated chains and the simulation of their frequency-dependent (third-harmonic generation, electroabsorption, and two-photon absorption) response. From the assignment of the calculated resonance features, the excited states dominating the third-order nonlinear polarizability are identified and their chain-length dependence is investigated. On that basis, we build an essential-state single-chain model (that includes the 1Bu, 2Ag, mAg, and nBu states) and apply it to the interpretation of recent experimental data reported for poly(paraphenylenevinylene) and derivatives. We then examine how the exciton binding energy, here defined as the difference between the energies of the charge-separated nBu and the strongly optically allowed 1Bu excited states, is affected by both intrachain and interchain polarization effects.

Original languageEnglish (US)
Pages (from-to)2829-2841
Number of pages13
JournalJournal of Chemical Physics
Issue number6
StatePublished - Aug 8 1999
Externally publishedYes

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


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