Total spin-state energy splittings are calculated for mono- and dications of the formula t[Re]-C-n-Re]}(z+) where [Re] = eta(5)-(C5Me5)Re(NO)(PPh3). C-n is an even-numbered carbon chain with n ranging from 4 to 20, and z is 1 or 2. These complexes are experimentally known, and their potential role as molecular electronic devices initiated this work. We have considered the different total spin states monocation/doublet, monocation/quartet, dication/singlet, and dication/triplet. Data obtained for two density functionals BP86 and B3LYP* were compared to verify the internal consistency of the results. In both ionization states, the low-spin state is the ground state, but the spin-state splittings decrease as the chain gets longer. For the dications, the splitting reaches a nearly constant value of about 10 kJ/mol with BP86 and about 4 KJ/mol with B3LYP* when there are at least 14 carbon atoms in the chain, whereas for the monocations, no constant value appears to be reached asymptotically, not even if 20 carbon atoms are in the chain, For monocations, the splittings range from 138 KJ/mol (n = 4) to 68 kJ/mol (n = 20) with BP86 and from 134 KJ/mol (n = 4) to 73 KJ/mol (n = 20) with B3LYP* and are thus considerably higher than those of the dications. The spin-state splittings are qualitatively mirrored by the energy splitting between the highest-occupied molecular orbital with beta spin (HOMObeta) and the lowest-unoccupied molecular orbital with (X spin (LUMOalpha) as obtained in the low-spin state. Furthermore, the HOMOalpha-LUMOalpha gaps decrease as the carbon chain lengthens. In addition, the local distribution of the, expectation value is analyzed for the monocation/doublet, the monocation/quartet, and the dication/triplet state using a modified Lowdin partitioning scheme. In the monocation/doublet and the dication/triplet state, the electron spin is distributed mainly on the metal centers and slightly delocalized onto the carbon chain. In the monocation/quartet state for chain lengths of more than 8 carbon atoms, the electron spin is mainly localized on selected atoms of the chain and not on the metal centers. In all cases, the spin delocalization onto the chain increases as the chain gets longer.