✍ Scribed by W.S. Hammack; H.G. Drickamer; D.N. Hendrickson
No coin nor oath required. For personal study only.
The effect of pressure on the optical charge-transfer (CT) band of the ion pair [Fe(CN),14-,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 G 1700 cm-' and the integrated intensity of the CT band increased by z 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 dccrcascd by over a factor of 2 at ambient pressure with increasing concentration of the ion pair (from I .O to 50 mM), correlating with the change of the ionic strength over this concentration range
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Infrared retlection-abso,rption spectra (IRAS) were taken from Au and Pt electrode surfaces which had been emersed from electrolytes containing the redox system Fe(CI@-W. The IRAS results show that the coverage of the electrodes with redox ions is smaller than has been suggested in the literature; s