Rotationally resolved photoelectron spectroscopy of the vanadium dimer Original Research Article

Results of calculations of the rotationally resolved photoelectron spectra of the V2+ ground state obtained by two-color excitation via the A3Πu ← X3Σg− system are reported and compared with recent pulsed-field-ionization zero-kinetic-energy measurements of these spectra. Agreement between the measured and calculated spectra is very encouraging. Both illustrate that the spin-orbit interaction plays an important role in photoionization of the A 3Πu state of V2 leading to the X4Σg− state of V2+. Striking differences are seen in the ion rotational distributions for ionization via the A 3Π1u and A 3Π2u spin-orbit components.