Intramolecular electron transfer in biferrocene monocation: evaluation of Franck-Condon effects via a time-dependent analysis of resonance Raman scattering in the extended near-infrared

Robert D. Williams, Vladimir I. Petrov, Hong Peter Lu, Joseph T Hupp

Research output: Contribution to journalArticle

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Abstract

Franck-Condon effects associated with intramolecular electron transfer in the biferrocene monocation have been evaluated via time-dependent analyses of resonance Raman scattering intensities and the intervalence absorption line shape. Quantitative studies in the extended near-infrared (1320 and 1064 nm excitation) reveal that three vibrational modes are displaced in the electron-transfer process. The most significant of these, the symmetrical ring-Fe-ring stretch, has also been implicated in prior X-ray crystallographic studies. Mode or bond displacements obtained from the Raman analysis are slightly larger than estimates based on crystallographic displacements. These differences together with contributions from two additional modes identified by Raman appear to account for seemingly disparate estimates of vibrational reorganization energies provided by (a) the crystallographic method and (b) 'Pekar plot' intercepts derived from intervalence absorption maxima. Implications for electron exchange kinetics are also discussed.

Original languageEnglish
Pages (from-to)8070-8076
Number of pages7
JournalJournal of Physical Chemistry A
Volume101
Issue number43
DOIs
Publication statusPublished - Jan 1 1997

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resonance scattering
Raman scattering
electron transfer
Raman spectra
Infrared radiation
Electrons
evaluation
rings
estimates
line shape
vibration mode
plots
kinetics
excitation
X rays
Kinetics
electrons
x rays
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Intramolecular electron transfer in biferrocene monocation : evaluation of Franck-Condon effects via a time-dependent analysis of resonance Raman scattering in the extended near-infrared. / Williams, Robert D.; Petrov, Vladimir I.; Lu, Hong Peter; Hupp, Joseph T.

In: Journal of Physical Chemistry A, Vol. 101, No. 43, 01.01.1997, p. 8070-8076.

Research output: Contribution to journalArticle

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