Marcus Theory of Electron Transfer 5: Two-Dimensional Bell-Shaped Marcus Curves

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This Demonstration compares the two-dimensional bell-shaped Marcus curves for the classical (blue) and semiclassical approach (yellow). The main difference, in the Marcus inverted region (at large negative values of ), is simple to observe and manipulate. Note that we show log
plots. The three-dimensional plots in earlier Demonstrations (see Related Links) are linear plots in the rate
. Note that at very low temperatures, both models become inaccurate.
Contributed by: René M. Williams (January 2023)
Open content licensed under CC BY-NC-SA
Snapshots
Details
Snapshot 1: data based on the work of Closs and Miller (focused here on the iso-octane data) at , with low solvent reorganization energies
Snapshot 2: for , the semiclassical Marcus equation behaves similarly to the CME
Snapshot 3: in the high temperature limit (1000 K), the semiclassical Marcus equation reduces to the CME
Snapshot 4: the very low temperature graph shows the effects of the summation factor: bell curves are added and shifted with increase of
Input data based on the work of Closs and Miller (focused here on the iso-octane data) at .
References
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