Abstract
The theory of maximum-overlap or Brueckner orbitals and of natural Orbitals is reviewed for closed-shell systems. A technique is described to calculate approximate Brueckner or natural orbitals for systems with a single valence electron, and this is applied together with the linked-diagram expansion of effective operators to evaluate the hyperfine interaction of some excited states of alkali atoms. It is found that it is in this way possible to reproduce reasonably well also the highly perturbed interactions of the excitedd states, which is not possible in a low-order expansion based on HF orbitals. Numerical results are given for the 5d state in K and the 4d state in Rb, where good experimental information is available.
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