3d photoionization along the xenon isoelectronic sequence

Abstract

The relativistic time-dependent density functional theory has been applied to3d photoionization along the Xe isoelectronic sequence, from I− to La3+.It is seen that interchannel coupling between the two spin–orbit photoionizationchannels greatly alters their partial photoionization cross sections. Changes similar tothose already observed for the Xe system are seen to affect the I−3d5/2partial cross section. For the elements following the noble gas in the isoelectronicsequence, Rydberg series of autoionization resonances associated withexcitations into the closed channels 3d3/2 → np1/2,3/2;n′f5/2are seen to strongly modulate the total and partial 3d5/2cross sections between the two spin–orbit split thresholds. Moreover, the analysisof the transfer of oscillator strength from the continuum to the discrete part of thespectrum along the series has permitted us to follow the occurrence of the collapseof the 4f wavefunction with a 3d hole, which is seen to occur already in Cs+.A global picture emerges from the comparison of 3d and 4d ionization in neutralsystems and Xe isoelectronic series.