Estimation of electron transfer parameters from AM1 calculations.

The utility of AM1 calculations for estimation of the electron-transfer parameters lambda'(v) (the enthalpy part of the Marcus internal reorganization energy) and H(ab) (the electronic coupling between the charge-bearing units) is considered for some charge-localized intervalence bis(hydrazine) radical cations, for which these parameters have been experimentally determined from optical measurements. The Koopmans estimate of lambda'(v) that employs the orbital separation for the neutral compound at the radical cation geometry is far from that calculated from the enthalpies of the species involved (eq 1) and is not correct. The eq 1 lambda'(v) enthalpies estimated by AM1 are reasonably good for compounds with only alkyl substituents but are overestimated by 33-59% for aryl-substituted hydrazines. The Koopmans estimate of H(ab) as half the orbital separation for the neutral species at the transition state geometry requires adjustment for the twist angles to those of the relaxed ground state to produce useful H(ab) values. Symmetry breaking occurs for the electron-transfer transition states of the compounds with saturated bridges, and the Koopmans estimate predicts H(ab) values that are slightly less than half as large as the optical measurements.