Rotationally resolved PFI-ZEKE photoelectron spectroscopic study of the low-lying electronic states of ArXe+.

Rotationally resolved pulsed-field-ionization zero-kinetic-energy photoelectron spectra of the X 1/2, A(1) 3/2, and A(2) 1/2 electronic states of the ArXe(+) molecular ion have been recorded following resonant (1+1') two-photon excitation via selected rovibrational levels of the C 1 and D 0(+) states of selected isotopomers of the ArXe molecule. Using rovibronic selection and propensity rules for the photoionization out of these intermediate molecular states enabled the determination of the parity of the molecular-ion levels and of the magnitude and sign of the Ω-doubling constants of the coupled X 1/2 (p ≈ 4B) and A(2) 1/2 (p ≈ -2B) states of ArXe(+). The results indicate that these molecular-ion states can be approximately described using Mulliken's second variant of Hund's angular momentum coupling case (c), for which J(a), the total electronic and spin angular momentum of the two atoms, is a good quantum number (semi-united atom). The analysis of the rotational structure enabled the derivation of improved values of the dissociation energies, equilibrium distances, and molecular constants for the X 1/2, A(1) 3/2, and A(2) 1/2 states of ArXe(+).