Abstract
Abstract Photo-double ionization of hydrogen iodide has been investigated over the photon energy range 29.0–32.5 eV by threshold photoelectrons coincidence (TPEsCO) spectroscopy and by ab initio calculations that included spin–orbit interaction. Good agreement is found between experiment and theory for the adiabatic ionization potentials for the formation of the X 3 Σ − , a 1 Δ and b 1 Σ + states of HI2+ and for the vibrational separations and relative vibrational intensities within the states. The spin–orbit splitting of the X 3 Σ − state of HI2+ is calculated to be 0.17924 eV for ν2+=0. Because this splitting is close to the calculated vibrational separations within the spin–orbit components of this state [e.g., for ν2+=0–1, 0.22382 eV in 3 Σ 0 − and 0.22163 eV in 3 Σ 1 − ], there is an overlapping of vibrational structure within the TPEsCO spectrum at the resolution used that is confirmed by the simulation spectrum.
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