The conductivity of polynuclear cluster situated between two metallic
electrodes is studied within the semiclassical approximation. The cond
uctivity depends on the shape of adiabatic potential surface of 'clust
er + excess electron' mixed-valence system which is entirely governed
by the relationship between the intramolecular electron transfer and t
he vibronic coupling. The specific cases of dimer and trimer molecules
are illustrated through conductivity and current calculations. It is
shown that localization --> delocalization transitions in mixed valenc
e clusters are accompanied by more or less abrupt changes in the molec
ular conductivity. However, the behavior of molecular conductivity and
tunnel current is determined not only by the type of electronic distr
ibution but also by the density of accessible electron-vibrational sta
tes. (C) 1998 Elsevier Science B.V.