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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 22, Number 7
BKCSDE 22(7)
July 20, 2001 

Cross-Interaction Constant and Intrinsic Reaction Barrier
Ikchoon Lee, Hai Whang Lee
Cross-interaction constant, Intrinsic barrier, Ritchie N+ equation, Marcus equation.
The cross second-derivative of the activation energy,ΔG , with respect to the two component thermodynamic barriers, ΔG˚X and ΔG˚Y, can be given in terms of a cross-interaction constant (CIC), βXYXY), and also in terms of the intrinsic barrier,ΔG。 , with a simple relationship between the two: βXY = -1/(6ΔG。). This equation shows that the distance between the two reactants in the adduct (TS, intermediate, or product) is inversely related to the intrinsic barrier. An important corollary is that the Ritchie N+ equation holds (for which βXY = 0) for the reactions with high intrinsic barrier. Various experimental and theoretical examples are presented to show the validity of the relationship, and the mechanistic implications are discussed.
732 - 738
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