Abstract
Sub-Doppler optical-optical double-resonance excitation spectra of BaF were recorded using two single-mode cw dye lasers. In the 30 000-cm−1 region, the electronic states observed were E2Σ+ and F2Π. The latter had been previously assigned as the “F2Σ+” state by Fowler [Phys. Rev.59, 645–652 (1941)]. The (3, 0) and (4, 0) bands of the E2Σ+-B2Σ+ transition and the (1, 0) and (2, 0) bands of the F2Π-B2Σ+ transition were rotationally analyzed. The molecular constants suggest inferences about the dominant atomic orbital character of the Rydberg molecular orbitals responsible for the E2Σ+ and F2Π electronic states. A new electronic state, the E′ 2Π, is predicted. The molecular parameters obtained (in cm−1, 1σ uncertainty in parentheses) are
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