Pressure Tuning Spectroscopic Study of Electron-Tunnelling Processes in Solution

Nita A. Lewis, Yaw S. Obeng, Daniel V. Taveras, Rudi Van Eldik

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Abstract

The first study of the effect of pressure on the intervalence transfer (IT) band of a very weakly coupled mixed valence binuclear, (μ-2,6-dithiaspiro[3.3]heptane)decaamminediruthenium(II,III) hexafluorophosphate in D2O is reported. A red shift of more than 200 cm-1 and a small increase in the oscillator strength of the IT band were observed over a pressure range of 1500 bars. These effects were interpreted as arising primarily from H-bonding between the ammine groups on the ruthenium atoms and the solvent D2O molecules. A nonadiabatic, multiphonon electron-tunnelling theory was employed to calculate rates of thermal electron transfer at each pressure, and ΔV was estimated to be -7.5 ± 0.2 cm3/mol for the thermal electron exchange.

Original languageEnglish (US)
Pages (from-to)924-927
Number of pages4
JournalJournal of the American Chemical Society
Volume111
Issue number3
DOIs
StatePublished - Feb 1989

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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