J. Conard et al., ELECTRONIC-PROPERTIES OF MXC60 AS SEEN BY NMR AND EPR AND COMPARED TOGRAPHITE-INTERCALATION COMPOUNDS, Journal of physics and chemistry of solids, 55(8), 1994, pp. 787-793
The knowledge of the wave function near the Fermi level is very import
ant to understand conductivity and superconductivity mechanisms. NMR a
nd ESR are able to describe how the wave function near E(F), shares am
ong the various atomic orbitals. The Knight shift measures the project
ion of the density of states at E(F) on the orbitals of the observed n
ucleus. So we prepared under vacuum the samples M(x) C60 with K, Rb(x
= 3) and Cs (x = 1,3) which were first characterized by X-rays, and Na
9.8C60 with the help of high pressure. In this paper we present the va
rious NMR shifts and lineshapes measured in our lab and concerning C-1
3 and alkali metals in M(x)C60 and RT ESR. We compare with similar mea
surements in GICs yet to be published. In M(x)C60 alkali compounds, th
e density of states at E(F) passes through a maximum at x = 3 which co
rresponds to the composition with the highest superconductive T(c) in
agreement with an e-phonon mechanism: The C-13 NMR spectra reveal esse
ntially a C(2p) state at E(F) with the same range of values for the de
nsity of states as for GICs, but with an additional shift resulting fr
om a small C(2s)-hybridization. Variable temperature Cs-133 spectra, a
nd RT ESR of the series K, Rb and Cs, with x = 3 are also compared to
GIC ones and show the same residual contribution of alkali s-orbital t
o the free electron wavefunction near E(F). An axial symmetry is seen
by Cs-133 in CsC60 with an important thermal shift. In low temperature
prepared Cs3C60, two sites at least are occupied by Cs, with a bad sy
mmetry. We evidenced at 25 K, 8.5 T, the superconductive transition in
Cs3C60 prepared at low temperature, and deduce some conclusions relat
ive to the origin of differences in T(c) between GICs and M(x)C60. We
conclude that the superconductive mechanism is a classical one, with a
good e-coupling to the hard ''in-plane'' longitudinal phonons thanks
to the C(2s)-hybridization near E(F). Annealing Cs3C60 at 380-degrees-
C destroys the superconductive phase and the stability domain of super
conductive Cs3C60 phase needs to be more precisely evaluated.