A dispersed fluorescence investigation of the low-lying electronic states of NiCu has allowed the observation of four out of the five states that derive from the 3d(Ni)(9) 3d(Cu)(10) sigma(2) manifold. Vibrational levels of the ground X-2 Delta(5/2) state corresponding to v = 0-11 are observed and are fit to provide omega(e) = 275.93 +/- 1.06 cm(-1) and omega(e)x(e) = 1.44 +/- 0.11 cm(-1). The v = 0 levels of the higher lying states deriving from the 3d(Ni)(9) 3d(Cu)(10) sigma(2) manifold are located at 912, 1466, and 1734 cm(-1), and these states are assigned to Q values of (3)/(2), (1)/(2), and (3)/(2), respectively. The last of these assignments is based on selection rules and is unequivocal; the first two are based on a comparison to ab initio and ligand field calculations and could conceivably be in error. It is also possible that the v = 0 level of the state found at 912 cm(-1) is not observed, so that To for the lowest excited state actually lies near 658 cm(-1). These results are modeled using a matrix Hanultonian based on the existence of a ground manifold of states deriving from the 3d(9) configuration on nickel. This matrix Hamiltonian is also applied to the spectroscopically well-known molecules AlNi, NiH, NiCl, and NiF. The term energies of the (2)Sigma(+), (2)Pi, and (2)Delta states of these molecules, which all derive from a 3d9 configuration on the nickel atom, display a clear and understandable trend as a function of the electronegativity of the ligands.