Complete characterization of the 3p Rydberg complex of a molecular ion: MgAr+. I. Observation of the Mg(3pσ)Ar+ B+ state and determination of its structure and dynamics.

We report on the experimental observation of the B+ 2Σ+ state of MgAr+ located below the Mg+(3p 2P3/2) + Ar(1S0) dissociation asymptote. Using the technique of isolated-core multiphoton Rydberg-dissociation spectroscopy, we have recorded rotationally resolved spectra of the B+ 2Σ+(v′) ← X+ 2Σ+(v″ = 7) transitions, which extend from the vibrational ground state (v′ = 0) to the dissociation continuum above the Mg+(3p 2P3/2) + Ar(1S0) dissociation threshold. The analysis of the rotational structure reveals a transition from Hund’s angular-momentum-coupling case (b) at low v′ values to case (c) at high v′ values caused by the spin–orbit interaction. Measurements of the kinetic-energy release and the angular distribution of the Mg+ fragments detected in the experiments enabled the characterization of the dissociation mechanisms. The vibrational levels of the B+ state above v′ = 6 are subject to predissociation into the Mg+(3p 2P1/2) + Ar(1S0) continuum, and the fragment angular distributions exhibit anisotropy β parameters around 0.5, whereas direct dissociation into the continuum above the Mg+(3p 2P3/2) + Ar(1S0) asymptote is characterized by β parameters approaching 2. Molecular ions excited to the B+ state with v′ = 0–6 efficiently absorb a second photon to the repulsive part of the 2Σ+ state associated with the Mg+(3d 2D3/2,5/2) + Ar(1S0) continua. The interpretation of the data is validated by the results of ab initio calculations of the low-lying electronic states of MgAr+, which provided initial evidence for the existence of bound vibrational levels of the B+ state and for the photodissociation mechanisms of its low vibrational levels.