Pressure Tuning Spectroscopic Study of Electron-Tunnelling Processes in Solution

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

doi:10.1021/ja00185a021

Pressure Tuning Spectroscopic Study of Electron-Tunnelling Processes in Solution

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

Chemistry

Research output: Contribution to journal › Article › peer-review

17 Scopus citations

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 language	English (US)
Pages (from-to)	924-927
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	111
Issue number	3
DOIs	https://doi.org/10.1021/ja00185a021
State	Published - Feb 1989

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "Pressure Tuning Spectroscopic Study of Electron-Tunnelling Processes in Solution",

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.",

author = "Lewis, {Nita A.} and Obeng, {Yaw S.} and Taveras, {Daniel V.} and Eldik, {Rudi Van}",

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AU - Lewis, Nita A.

AU - Obeng, Yaw S.

AU - Taveras, Daniel V.

AU - Eldik, Rudi Van

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N2 - 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.

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