The 3dNi8(3F)3dCu10σ2σ*1 manifold of excited electronic states of NiCu

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Abstract
Diatomic NiCu has been supersonically cooled in a molecular beam and investigated by resonant two‐photon ionization spectroscopy. A total of nine band systems connecting the ground 3d9Ni3d10Cuσ2, X 2Δ5/2 state to the 3d8Ni(3F)3d10Cuσ2σ*1 manifold of states have been found, and bands of eight of these systems have been rotationally resolved and analyzed. L‐ and S‐uncoupling interactions have been found between two pairs of states, resulting in B[11.9]2.5∼C[11.9]1.5 and [10.4]2.5∼[10.4]1.5(?) heterogeneous perturbations. In the case of the B∼C interaction, the magnitude of the perturbation matrix element has been deduced. The detailed spectroscopic analysis of the 3d8Ni(3F)3d10Cuσ2σ*1 manifold of states presented in this paper allows the electronic structure of NiCu to be understood in depth and provides a database for comparison to the ligand‐field plus spin–orbit calculation of the NiCu excited states presented in the following paper.