2.

3 Many-Electron Ions 37

The non-relativistic part contains the sum of the one-electron terms,

and the all-important Coulomb repulsion between the electrons

Extensive work on the two-electron case (the He atom, the H- ion,

etc.) has uncovered a complicated structure of the wave function. A
full solution for more than two electrons is hopeless or impracticable.
However, we will take it for granted that a mean-field solution (obtained
in the Hartree-Fock approximation) gives at least a good starting point.
In this approach one assumes that, in addition to the field 4(r) of the
nucleus, each electron feels also the spherically symmetrical average field
of the other electrons, so that it will move in some hydrogen-like orbit.
Using the Pauli principle, we construct the ground state by filling the
lowermost available states. Thus we arrive at the concept of the ground
state eonfigurationof an atom: it is a list of the occupied states, labelling
them with the names of hydrogenic orbitals. For instance, the sodium
atom has the configuration 1 ~ ~ 2 9 ~ 2 p ~ However,
39'. such full lists are
seldom given. Conveying the idea that inner shells with a noble gas
configuration form an imperturbable part of the ion core, we may also
say that Na has the configuration [Ne]3s1, or simply 3s1.
What is left out in this scheme? It is just the possibility that config-
urations may get mixed. The interaction term 3Cel-el has non-vanishing
matrix elements between any two two-electron states if they have the
same values of the relevant quantum numbers. Thus, for example's sake,
the l D state (S = 0, L = 2) may be realized either in a nls1n2d1 config-
uration, or in a nlp1n2p1 configuration. It follows that the configuration
nlslnzd' does not appear pure, but has an admixture of nlp'n2p' con-
figurations. We trust that such effects are usually weak and will refer
to them only occasionally".
In what follows, we discuss the level structure belonging to a given
configuration. First, let us consider two electrons in the same shell,
"At least in our present discussion. Since atoms have discrete spectra, configu-
ration mixing has to act across large energy differences, and therefore it is a weak
effect. In solids, a vast number of states lie infinitesimally close, and the story may
be different.Ch. 9 will be devoted to what is essentially a configuration interaction
calculation for the Hubbard model.