title: Monoligated monovalent Ni: the 3d(Ni)9 manifold of states of NiCu and comparison to the 3d9 States of AlNi, NiH, NiCl, and NiF.
abstract: 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 sigma2 manifold. Vibrational levels of the ground X2delta(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 sigma2 manifold are located at 912, 1466, and 1734 cm(-1), and these states are assigned to omega 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 T0 for the lowest excited state actually lies near 658 cm(-1). These results are modeled using a matrix Hamiltonian based on the existence of a ground manifold of states deriving from the 3d9 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 2sigma+, 2pi, and 2delta 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.
authors.affiliation: Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, USA.
authors.forename: Gretchen K
authors.initials: GK
authors.lastname: Rothschopf
authors.forename: Michael D
authors.initials: MD
authors.lastname: Morse