Rh. Herber et Tp. Hanusa, HYPERFINE INTERACTIONS AND LATTICE-DYNAMICS OF FERROCENE, RING-SUBSTITUTED FERROCENES AND THEIR OXIDATION-PRODUCTS, Hyperfine interactions, 108(4), 1997, pp. 563-575
Using Fe-57 Mossbauer spectroscopy over the range 90 less than or equa
l to T less than or equal to 290 K, the isomer shift (IS) and quadrupo
le splitting (QS) hyperfine parameters have been determined for ferroc
ene and a number of ring-substituted ferrocenes, as well as for their
cationic oxidation products, in order to elucidate the temperature dep
endencies of these parameters for such complexes. As noted previously,
the IS is not sensitive to ring substitution, but its temperature dep
endence can be used to estimate an ''effective vibrating mass'' (M-eff
) as probed by the resonance effect. In conjunction with the temperatu
re dependence of the recoil-free fraction, it is Possible to estimate
a ''Mossbauer lattice temperature'', (Theta(M)), for these solids. The
QS parameter is temperature insensitive over the cited range for all
of the neutral complexes. The cationic species give rise to a broad re
sonance which can be understood in terms of a spin 1/2 relaxation whic
h is fast on the Mossbauer time scale. The temperature dependencies of
the IS and recoil-free fraction for these relaxation spectra are also
reported in detail.