Abstract
Though one would expect that large-angular momentum doubly excited states exhibit weak electronic correlations, it is shown in this paper that a first-order perturbation theory ignoring such correlations may completely fail in predicting correct autoionization probabilities: quadrupolar transitions are poorly described by lowest-order perturbation theory, except for very large angular momenta. Inclusion of second-order dipole-dipole term considerably improves the accuracy of the method. This effect is computed using Coulomb Green’s function in its analytical form, probably applied here for the first time to autoionization processes. Examples are given in barium for 5dj 5g [k] states (j = 3/2, 5/2) and for 5d5/2nl [k] states with l > 4.
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