In relation to the known complexes Pd-2(CNMe)(6)(2+) and Pd-2(CN-t-Bu)(4)Cl-2, Pd-2(tmb)(2)Cl-2 (tmb = 2,5-dimethyl-2’,5’-diisocyanohexane) and Pd-3(dppm)(3)CO2+ (dppm = ((C6H5)(2)P)(2)CH2), respectively, the ground and lowest energy triplet excited state geometries of the model compounds Pd-2(CNMe)(4)Cl-2 and Pd-2(CN(CH2)(4)NC)(2)Cl-2, and Pd-3(PH3)(6)CO2+ have been optimized using density functional theory. The computations for ground state structures are in excellent agreement with the X-ray data. In the excited states, bond lengthening (due to the change in Pd-Pd bond order 0 --> 1) is predicted. In the bridged species, Pd-2(CN(CH2)(4)NC)(2)Cl-2, the computations reveal that twisting of the dihedral angle must occur in order to account fur the large change in Pd-Pd distance. Finally, the Pd-Pd bond lengthening for the Pd-3(dppm)(3)CO2+ cluster in the (3)A(2) excited state is predicted to be similar to 0.19 Angstrom relative to the ground state. This value has also been confirmed by an analysis of the emission band using Heller’s time-dependent theory.