Fast electron transfer reactions in a rigid matrix; Further evidence for quantum mechanical tunneling
✍ Scribed by John R. Miller
- Publisher
- Elsevier Science
- Year
- 1973
- Tongue
- English
- Weight
- 309 KB
- Volume
- 22
- Category
- Article
- ISSN
- 0009-2614
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✦ Synopsis
Trapped electrons in aqueous 6hI NaOII ut 77°K are observed to react with solutes over the wide time range 1 II-* set (and probably much shorter times) to minutes. The kinetics are in accord with a tunneling reaction mechanism.
Recently, experimental evidence [I] has been found that electrons trapped in organic glasses react by quantum mechanical tunneling through tens of angstroms orinert solvent to reach electron accepting molecules. The model used predicted that such reactions would have observable kinetic components ranging from nanoseconds to minutes in a single sample. Observation of such a reaction in a rigid organic glass, using millisecond flash photolysis, has been reported [21.
ton and co-workers down to 175'K. They concluded that the rate constants tend to zero at the glass transition temperature, 135°K [4]. Thus the observation of significant time dependent reactions at 77OK is surprising.
This communication
describes results of pulse radiolysis experiments using 3 to 12 nsec pulses of 3 Mev electrons to produce ionization in aqueous 6M NaOH at 77°K. In the absence of electron accepting