Ab initio quantum calculation of the diabatic coupling matrix elements for the self-exchange redox couples M(Cp)20/+ (M = Fe, Co; Cp = C5H5).
The diabatic couplings between the metal centers in M(Cp)20/+ (M = Fe, Co; Cp = C5H5) were evaluated using ab initio methods at the Hartree-Fock level of theory. Excellent agreement with the experimental estimate is found for the Fe(Cp)20/+ couple. For Co(Cp)20/+, the calculated numbers are substantially higher than the experimental estimates, suggesting that the latter may represent a considerable underestimate (a possibility mentioned in the experimental publication).
Baik
Mu-Hyun
MH
Department of Chemistry, Columbia University, New York, New York 10027, USA.
Crystal
Joseph B
JB
Friesner
Richard A
RA