High resolution rotational analysis of the B 3Π–X 3Δ (1,0) band of titanium monoxide

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Abstract
The B 3Π–X 3Δ (1,0) band of titanium monoxide has been studied at sub‐Doppler resolution (0.002 cm−1) by crossing a beam of TiO molecules with a cw tunable laser beam and by collecting the laser‐induced fluorescence. The rotational structure of 42 branches belonging to the 3Π–3Δ transition has been analyzed up to rotational quantum numbers equal to 94. Spectroscopic data have been reduced to a set of 24 molecular constants, using a case (a) effective Hamiltonian. The rotational, spin–orbit and Λ‐doubling constants are discussed in terms of the leading configurations which give rise to the X 3Δ and B 3Π electronic states. It is shown that for the B state, existing ab initio calculations are not able to reproduce the second order spin–orbit effect and the Λ doubling effect.

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