Effect of pressure on the charge-transfer band of the [Fe(CN)6]4-·dimethyl viologen ion pair

W. S. Hammack, H. G. Drickamer, D. N. Hendrickson

Research output: Contribution to journalArticlepeer-review


The effect of pressure on the optical charge-transfer (CT) band of the ion pair [Fe(CN)6]-4·DMV2+ (DMV = dimethyl viologen) has been studied in aqueous solution. In the pressure range 0.001 to 10.0 kbar the CT band maximum shifted to higher energy by ≈1700 cm-1 and the integrated intensity of the CT band increased by ≈35%, with no change in the peak width. These results accord with a vibronic coupling model describe to mixed-valence metal compounds, with a general theory of absorption spectra of ions in solution, as well as with Mulliken's theory of charge transfer. The oscillator strength of the CT band decreased by over a factor of 2 at ambient pressure with increasing concentration of the ion pair (from 1.0 to 50 mM), correlating with the change of the ionic strength over this concentration range.

Original languageEnglish (US)
Pages (from-to)469-473
Number of pages5
JournalChemical Physics Letters
Issue number4-5
StatePublished - Oct 21 1988

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry


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