Fine and hyperfine resolved empirical energy levels of VO

•A MARVEL analysis of 6 quartet and 7 doublet states of VO yields 4641 empirical energy levels•A separate analysis of hyperfine-resolved transtions gives 4393 levels with hyperfine structure•191 lines are assigned the 2 - X intercombination band system A MARVEL (measured active rotational-vibrational energy levels) analysis of the spectra of vanadium oxide (VO) is performed, involving thirteen electronic states (6 quartets and 7 doublets). 51V16O data from 14 sources are used to form three networks: hyperfine-resolved quartets, hyperfine-unresolved quartets and hyperfine-unresolved doublets. A single quartet network is formed by deperturbing the hyperfine lines and 191 lines are assigned to an intercombination 2 2Π–X 4Σ− band system in the visible region previously recorded by Hopkins et al. (J. Chem. Phys. 130 (2009) 144308), allowing the doublet and quartet networks to be merged. As a result 6 603/4 402 validated transitions/final energies were obtained from analysis of the hyperfine-resolved network and 9 087/4 712 from the unresolved. Tv energy values and other molecular constants are determined for all doublet states within the networks.