23 - Double Rydberg states

Summary

The autoionizing two electron states we have considered so far are those which can be represented sensibly by an independent electron picture. For example, an autoionizing Ba 6pnd state is predominantly 6pnd with only small admixtures of other states, and the departures from the independent electron picture can usually be described using perturbation theory or with a small number of interacting channels. In all these cases one of the electrons spends most of its time far from the core, in a coulomb potential, and the deviation of the potential from a coulomb potential occurs only within a small zone around the origin.

In contrast, in highly correlated states the noncoulomb potential seen by the outer electron is not confined to a small region. In most of its orbit the electron does not experience a coulomb potential, and an independent electron description based on nℓn′ℓ′ states becomes nearly useless. There are two ways in which this situation can arise. The first, and most obvious, is that the inner electron's wavefunction becomes nearly as large as that of the outer electron. If we assign the two electrons the quantum numbers n_iℓ_i and n_oℓ_o, this requirement is met when n_i approaches n_o, which leads to what might be called radial correlation. The sizes of the two electron's orbits are related. The second way the potential seen by the outer electron can have a long range noncoulomb part is if the presence of the outer electron polarizes the inner electron states.