Theoretical study of the spin-orbit autoionization in molecules application to the HI photoionization spectrum

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Abstract
A theoretical study of the spin-orbit autoionization in molecules with 2Π state ion cores is presented. The multichannel quantum defect theory is used with an ab initio calculation of the relevant electronic quantities. In the application to the HI photoionization spectrum the energy positions of the observed resonances between the 2Π1/2 and 2Π3/2 ionization thresholds are well reproduced. The importance of the l mixing especially for the π3σ channels is stressed. An attempt to include the S-uncoupling part of the rotational operator in the calculations gives rise to additional autoionization peaks, associated with a new type of rotational autoionization specific to 2Π-state cores. Theoretical predictions are also made for the angular distribution and spin polarization parameters of the photoelectron in the 1155–1168 Å energy range.