Complete characterization of the 3p Rydberg complex of a molecular ion: MgAr⁺. II. Global analysis of the A⁺ ²Π and B⁺ ²Σ⁺ (3pσ,π) states

Génévriez, Matthieu [UCL] Wehrli, Dominik [Laboratory of Physical Chemistry, ETH Zurich, CH-8093 Zurich, Switzerland] Merkt, Frédéric [Laboratory of Physical Chemistry, ETH Zurich, CH-8093 Zurich, Switzerland]

We report a global study of the 3p Rydberg complex of the MgAr+ molecular ion. High-resolution spectroscopic data on the two spin–orbit components of the A+ electronic state were obtained by isolated-core multiphoton Rydberg-dissociation spectroscopy up to vibrational levels as high as v′ = 29, covering more than 90% of the potential wells. Accurate adiabatic potential-energy functions of the A+ and B+ states, which together form the 3p Rydberg complex, were obtained in a global direct-potential-fit analysis of the present data and the extensive data on the B+ state reported in Paper I [D. Wehrli et al., J. Chem. Phys. 153, 074310 (2020)]. The dissociation energies of the B+ state, the two spin–orbit components of the A+ state, and the X+ state of MgAr+ are obtained with uncertainties (1 cm−1) more than two orders of magnitude smaller than in previous studies.