Reorganization Energy and ET

1
Reorganization Energy and ET

• Experiments show that FAAQ has a long lived ET
  excited state (gt900 ms), but the corresponding
  state in FcFAAQ decays rapidly (20 ps)a
• Cyclic voltammetry measurements give
  DG(FAAQ)2.24 eV and DG(FcFAAQ)1.12 eV
• Using CDFT (B3LYP/6-31G), one finds
• In inverted region, larger gap for FAAQ means
  longer lifetime

FAAQ
FAAQ FcFAAQ DGsol 2.36 eV 1.12
eV liCT .34 eV .35 eV li0 .34 eV
.35 eV
FcFAAQ
D-A-
D-A
aOkamoto et al., J. Phys. Chem. 109, 4662 (2005).