Adiabatic Electron Transfer: Comparison of Modified Theory with Experiment
Stephen F. Nelsen,
*
Rustem F. Ismagilov,
Dwight A. Trieber II
The radical cations of properly designed bishydrazines allow
comparison of observed and calculated electron transfer rate constants.
These compounds have rate constants small enough to be measured by
dynamic electron spin resonance spectroscopy and show charge transfer
bands corresponding to vertical excitation from the energy well for the
charge occurring upon one hydrazine unit to that for the
electron-transferred species. Analysis of the data for all six
compounds studied indicates that the shape of the adiabatic surface on
which electron transfer occurs can be obtained from the charge transfer
band accurately enough to successfully predict the electron transfer
rate constant and that explicit tunneling corrections are not required
for these compounds.
Department of Chemistry, University of Wisconsin, Madison, WI
53706-1396, USA.
*
To whom correspondence should be addressed. E-mail:
nelsen{at}chem.wisc.edu
