Journal of the American Chemical Society p. 887 - 893 (1992)
Update date:2022-08-12
Topics:
Han, Chau-Chung
Wilbur, James L.
Brauman, John I.
Rate constants for gas-phase electron-transfer reactions between substituted nitrobenzenes have been measured using ion cyclotron resonance spectroscopy. On the basis of the assumption that these reactions occur through the formation of an intermediate complex, a statistical model is used to interpret the reaction kinetics. The intersecting parabolas quantum mechanical model provides an alternative description of the energy surface. Energy barriers are found to be consistent for the two methods. The results for exothermic reactions are consistent with a Marcus theory analysis, but suggest that a zero-order potential energy surface may not be completely adequate for quantitative prediction of reaction rates.
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