The electron transfer properties of the mixed-valence biferrocenium cation are investigated using the Piepho-Krausz-Schatz (PKS) vibronic theory. Parameters of the model are deduced from both vibrational spectroscopy (stiffness constant) and MO calculations (transfer integral and vibronic coupling parameter); the computed asymmetric distortion agrees with structural data; a specific heat Schottky anomaly, recently reported, is also explained in the frame of that model. The low-temperature transfer rate is also computed. It ranges from 1.5 x 10(10) to 8.7 x 10(12) s-1, according to the nature of the HOMO, and definitively lies higher than the Mossbauer timescale (almost-equal-to 10(8) s-1).
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[1]
BABONNEAU F, 1984, THESIS U PARIS 6
[2]
BOUKHEDDADEN K, IN PRESS J PHYS B
[3]
BOUSSEKSOU A, 1992, J PHYS I, V2, P1381, DOI 10.1051/jp1:1992217