Journal of Physical Chemistry p. 10535 - 10537 (1991)
Update date:2022-08-16
Topics:
Blackbourn, Robert L.
Johnson, Christopher S.
Hupp, Joseph T.
Bryant, Mark A.
Sobocinski, Raymond L.
et al.
A complete experimental description of the vibrational Franck-Condon barrier to the one-electron reduction of 4-cyano-N-methylpyridinium cation (NC-py-Ch3+) has been obtained.Because of the chemical irreversibility of the electron transfer, the reaction is not readily amenable to study by conventional structural methods.The approach successfully employed here, however, was a time-dependent analysis of near-resonant Raman scattering where resonance was achieved by pairing the cation to iodide anion; the pairing gives rise to a weak (ε = 565 M-1cm-1) outer-sphere charge-transfer band centered at 428 nm in acetonitrile as solvent.The time-dependent analysis of scattering yields vibrational frequencies, coordinate displacements, and single-mode barrier contributions for each of 13 modes involved in outer-sphere electron transfer.Depolarization measurements, excitation profiles, and scattering studies with the nonchromophoric
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