Origin of High Second- and Third-Order Nonlinear Optical Response in Ammonio/Borato Diphenylpolyene Zwitterions: The Remarkable Role of Polarized Aromatic Groups

Victor M. Geskin, Christoph Lambert*, Jean-Luc Bredas

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

462 Scopus citations

Abstract

We present a quantum-chemical analysis of the molecular structure and second- and third-order polarizabilities in a series of promising nonlinear optical (NLO) chromophores, the zwitterionic ammonio/borato diphenylpolyenes, R3N+Ph(C=C)nPhB-R3, whose synthesis has been reported recently. The molecular geometries are obtained via MP2/6-31G optimization, while the NLO properties are calculated with the INDO Hamiltonian using the sum-over-states and finite-field real-space methods. The real-space approach allows the direct evaluation of the NLO-active segments of the molecules, while the sum-over-states results illustrate the virtual excitations and charge-transfer pathways that are essential in the NLO response. Both methods highlight the remarkable and unexpected result that it is the strongly polarized phenylene groups that play the key role in generating a high NLO response.

Original languageEnglish (US)
Pages (from-to)15651-15658
Number of pages8
JournalJournal of the American Chemical Society
Volume125
Issue number50
DOIs
StatePublished - Dec 17 2003

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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