Anomalous second-order nonlinear optical response of in-plane poled glassy polymers. Spectroscopic and theoretical support for the importance of charged chromophore aggregates

Shlomo Yitzchaik, Santo Di Bella, Paul M. Lundquist, George K. Wong, Tobin J Marks

Research output: Contribution to journalArticle

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Abstract

We report here measurements of the orientational and frequency dependence of the anomalously large second-order nonlinear optical (NLO) susceptibilities observed in guest-host DANS [4-(N,N-dimethylamino)-4'-nitrostilbene]/PMMA [poly(methyl methacrylate)] films poled in an 'in-plane' electrode configuration. The resonant response is sharply peaked (fwhm decreases by a factor of 4) in comparison to identical samples poled by standard corona field techniques. Additionally, these anomalous susceptibilities, which are oriented normal to the electric poling field, exhibit unusually strong features at long wavelengths where the linear absorption is low. We also report the first direct experimental EPR evidence for nitrogen-centered cation radicals, hence the creation of charged chromophores trapped in the polymeric matrix by charge injection from the poling electrodes. These observations are in qualitative agreement with the very large NLO response magnitudes and distinct spectral features predicted by sum-over-states perturbative calculations performed for positively charged centrosymmetric chromophore dimers and provide strong computational evidence that the observed anomalous NLO response is due to charged chromophore aggregates.

Original languageEnglish
Pages (from-to)2995-3002
Number of pages8
JournalJournal of the American Chemical Society
Volume119
Issue number13
DOIs
Publication statusPublished - Apr 2 1997

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Chromophores
Polymers
Electrodes
Polymethyl Methacrylate
Cations
Charge injection
Nitrogen
Polymethyl methacrylates
Dimers
Injections
Paramagnetic resonance
Positive ions
Electric fields
Wavelength
4-methoxymethamphetamine

ASJC Scopus subject areas

  • Chemistry(all)

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Anomalous second-order nonlinear optical response of in-plane poled glassy polymers. Spectroscopic and theoretical support for the importance of charged chromophore aggregates. / Yitzchaik, Shlomo; Di Bella, Santo; Lundquist, Paul M.; Wong, George K.; Marks, Tobin J.

In: Journal of the American Chemical Society, Vol. 119, No. 13, 02.04.1997, p. 2995-3002.

Research output: Contribution to journalArticle

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AU - Marks, Tobin J

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N2 - We report here measurements of the orientational and frequency dependence of the anomalously large second-order nonlinear optical (NLO) susceptibilities observed in guest-host DANS [4-(N,N-dimethylamino)-4'-nitrostilbene]/PMMA [poly(methyl methacrylate)] films poled in an 'in-plane' electrode configuration. The resonant response is sharply peaked (fwhm decreases by a factor of 4) in comparison to identical samples poled by standard corona field techniques. Additionally, these anomalous susceptibilities, which are oriented normal to the electric poling field, exhibit unusually strong features at long wavelengths where the linear absorption is low. We also report the first direct experimental EPR evidence for nitrogen-centered cation radicals, hence the creation of charged chromophores trapped in the polymeric matrix by charge injection from the poling electrodes. These observations are in qualitative agreement with the very large NLO response magnitudes and distinct spectral features predicted by sum-over-states perturbative calculations performed for positively charged centrosymmetric chromophore dimers and provide strong computational evidence that the observed anomalous NLO response is due to charged chromophore aggregates.

AB - We report here measurements of the orientational and frequency dependence of the anomalously large second-order nonlinear optical (NLO) susceptibilities observed in guest-host DANS [4-(N,N-dimethylamino)-4'-nitrostilbene]/PMMA [poly(methyl methacrylate)] films poled in an 'in-plane' electrode configuration. The resonant response is sharply peaked (fwhm decreases by a factor of 4) in comparison to identical samples poled by standard corona field techniques. Additionally, these anomalous susceptibilities, which are oriented normal to the electric poling field, exhibit unusually strong features at long wavelengths where the linear absorption is low. We also report the first direct experimental EPR evidence for nitrogen-centered cation radicals, hence the creation of charged chromophores trapped in the polymeric matrix by charge injection from the poling electrodes. These observations are in qualitative agreement with the very large NLO response magnitudes and distinct spectral features predicted by sum-over-states perturbative calculations performed for positively charged centrosymmetric chromophore dimers and provide strong computational evidence that the observed anomalous NLO response is due to charged chromophore aggregates.

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