Spin-orbit selectivity observed for the HCl+ ((X)over-tilde (II)-I-2) state using resonant photoemission

We report the experimental observation of a strongly selective population of the spin-orbit components in the HCl+ (X) over tilde (2)Pi(Omega) states after excitation into the dissociative 2p(-1)6sigma* core excited state. A progression of highly excited vibrational states with either the Omega=3/2 or Omega=1/2 component of the final state is populated, respectively, when the excitation is tuned in the 2p(3/2)(-1)6sigma*or2p(1/2)(-1)6 sigma* part of the resonance. This effect is explained theoretically to be due to the orientational selectivity of the excitation process and the preference of the L-2,L-3 VV Auger process to produce valence holes with the same orientation as the core holes.