Renormalized atom method shell

The calculation of 4f promotion energy requires the combination of an atomic calculation for the 4f shell and a band calculation for the 5d band. The two calculations are based on such drastically different approximations that the combination of the two under one algorithm is a seemingly impossible task. Herbst et al. (1972) overcame this difficulty by using the renormalized atom method first proposed for the d band metals by Watson et al. (1970) and reported in detail by Hodges et al. (1972). We will review here the philosophy of the method, with particular emphasis on the meaning of the various approximations. The computational details are found in the original article. The relativistic version of the calculation has been published recently by Herbst et al. (1976). 

Although P3 procedures perform well for a variety of atomic and molecular species, caution is necessary when applying this method to open-shell reference states. Systems with broken symmetry in unrestricted Hartree-Fock orbitals should be avoided. Systems with high multireference character are unlikely to be described well by the P3 or any other diagonal approximation. In such cases, a renormalized elec-... 

---