Dye laser excitation and fluorescence spectra have been used to provide information on rotational structure and energy linkages between several low‐lying electronic states of YbO. Configurational assignments of the observed low‐lying states have been made on the basis of vibrational frequencies. The X1Σ+ ground state, with ΔG1/2=683 cm−1, is assigned to the Yb2+ 4f14 configuration, whereas five states with Ω=0, 1, 2, 1, and 3 and ΔG1/2∼820–830 cm−1 are assigned to Yb2+ 4f136s. The lowest 4f136s(Ω=0) state is found to be 910 cm−1 above the 4f14, X1Σ+ state, thus establishing the linkage between the  f14 and  f13s configurations. The observed electronic states are discussed in relation to the ligand field model and the electronic state energies are fitted to determine the ligand field parameters. The configurational assignment for the YbO ground state proposed by M. Dolg and H. Stoll [Theor. Chim. Acta 75, 369 (1989)] is shown conclusively to be incorrect.

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