Giant dipole moment in a triad system. Mechanisms of anisotropic photoresponse in the transient dc conductivity of dipolar solutes

Sergei N. Smirnov, Charles L. Braun, Scott R. Greenfield, Walter A. Svec, Michael R Wasielewski

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Abstract

A transient dc conductivity method was used to observe formation of a giant dipole moment for the triad molecule MA-ANI-NI (methoxyaniline-aminonaphthalimide-dimethylphenyl-naphthalenediimide-octyl) in toluene. The independence of the dipole moment on excitation wavelength indicates high efficiency of intramolecular energy or (and) electron transfer. The effect of light polarization on the DC conductivity signal caused by a photoinduced increase in solute dipole moment is considered in detail. It is shown that the time variation of the signal includes information about structural anomalies in the angular distribution function of molecular dipoles and depends on light polarization even for zero ground state dipole moment. Nonzero ground state dipole moment and (or) electric field dependence of the charge transfer rate constants give an additional source for an anisotropic photoresponse signal. Analysis of the photoresponse and its anisotropy for the triad gives ground (μg), first (μ1), and second (μ2) excited state dipole moments as follows: μg = 12 ± 5 D, μ1 = 35 ± 10, and μ2 = 87 ± 6 D. The lifetime of the giant dipole state is τ = 290 ± 10 ns, and the molecule's rotational time is τr = 1.6 ± 0.15 ns.

Original languageEnglish
Pages (from-to)12329-12336
Number of pages8
JournalJournal of Physical Chemistry
Volume100
Issue number30
Publication statusPublished - Jul 25 1996

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Dipole moment
solutes
dipole moments
conductivity
Light polarization
Ground state
dipoles
Molecules
ground state
Angular distribution
Toluene
polarization
Excited states
excitation
Distribution functions
toluene
Charge transfer
molecules
Rate constants
electron transfer

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Engineering(all)

Cite this

Giant dipole moment in a triad system. Mechanisms of anisotropic photoresponse in the transient dc conductivity of dipolar solutes. / Smirnov, Sergei N.; Braun, Charles L.; Greenfield, Scott R.; Svec, Walter A.; Wasielewski, Michael R.

In: Journal of Physical Chemistry, Vol. 100, No. 30, 25.07.1996, p. 12329-12336.

Research output: Contribution to journalArticle

Smirnov, Sergei N. ; Braun, Charles L. ; Greenfield, Scott R. ; Svec, Walter A. ; Wasielewski, Michael R. / Giant dipole moment in a triad system. Mechanisms of anisotropic photoresponse in the transient dc conductivity of dipolar solutes. In: Journal of Physical Chemistry. 1996 ; Vol. 100, No. 30. pp. 12329-12336.
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