Structure and dynamics of H2+ near the dissociation threshold: A combined experimental and computational investigation

© 2016 Elsevier Inc.The pulsed-field-ionization zero-kinetic-energy photoelectron spectrum of H2 has been recorded in the vicinity of the dissociative-ionization threshold following three-photon excitation via selected rotational levels of the B 1Σu+(v = 19) and H‾ 1Σg+(v = 11) intermediate states. The spectra consist of transitions to bound levels of the X+ 2Σg+ state of H2+ with v+ in the range 14–19 and N+ in the range 0–9, of the A+ 2Σu+ state with v+ = 0 and N+ = 0–2, and of shape resonances corresponding to the X+(v+ = 17, N+ = 7) and X+(v+ = 18, N+ = 4) quasibound levels. Calculations of the level structure of H2+ have been carried out and the influence of adiabatic, nonadiabatic, relativistic and radiative corrections on the positions of these levels, and in the case of the shape resonances also on their widths, has been investigated. Different methods of calculating the widths and profiles of the shape resonances have been tested for comparison with the experimental observations. Slow oscillations of the dissociative-ionization yield have been observed and reflect, in first approximation, the Franck-Condon factors of the X+, A+←H‾ bound - free transitions.