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We have determined the excess polarizability of the relaxed first excited-singlet-state S₁ on isolated chains of phenylene-vinylene oligomers and polymers by measuring the transient change in the microwave dielectric constant that occurs on flash photolysis of dilute solutions. The isotropic value of the excess polarizability volume, Δα^'(S₁), increases from 250 ³ for a dimer to 960 ³ for an octamer, and 1600 ³ for high molecular weight polymers. The value for the isolated polymer is close to that found for the unrelaxed S₁ state in electroabsorption (Stark effect) measurements on solid samples of poly(phenylene-vinylene), indicating that exciton delocalization is not strongly influenced by either post-excitation relaxation of the polymer backbone geometry, or by interchain interactions.
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Gelinck et al. (2000) studied this question.
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