Optical electron transfer processes. The dependence of intervalence line shape and transition energy on chromophore concentration

Robert L. Blackbourn, Joseph T Hupp

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

Optical electron transfer in the mixed-valence cation of biferrocenylacetylene (BF+) has been examined in CD2Cl2 solvent. The intervalence absorption line shape is relatively narrow at both low and high chromophore concentrations, but broader at intermediate concentrations. The transition energy for metal-to-metal charge transfer increases from ≈4440 cm-1 at infinite dilution to 5995 cm-1 for 3.8 mM BF+. Related effects exist due to added electrolyte. Neither the electrolyte nor chromophore concentration effects are expected from a simple reading of electron transfer theories. Nevertheless, both phenomena can be understood and within the context of theory upon careful consideration of the effects of ion-pairing (and tripling) equilibria upon electron-transfer energetics.

Original languageEnglish
Pages (from-to)399-405
Number of pages7
JournalChemical Physics Letters
Volume150
Issue number6
DOIs
Publication statusPublished - Sep 23 1988

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Chromophores
Electron transitions
chromophores
line shape
electron transfer
Electrolytes
Electrons
Metals
electrolytes
metals
Dilution
dilution
energy
Cations
Charge transfer
charge transfer
Ions
valence
cations
ions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Condensed Matter Physics
  • Atomic and Molecular Physics, and Optics
  • Surfaces and Interfaces

Cite this

Optical electron transfer processes. The dependence of intervalence line shape and transition energy on chromophore concentration. / Blackbourn, Robert L.; Hupp, Joseph T.

In: Chemical Physics Letters, Vol. 150, No. 6, 23.09.1988, p. 399-405.

Research output: Contribution to journalArticle

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