In the present approach the high reliability of ab initio techniques is combined with the easily amenable phenomenological core polarization concept for an efficient treatment of intershell correlation effects in all-electron SCF and valence CI calculations. By use of only a single adjustable atomic parameter, which is related to the radius of the core and determines the cutoff at short range, our effective core polarization potential (CPP) accounts quantitatively for dynamical intershell correlation as well as exclusion effects on the correlation energy of the core. The applications refer to alkali and alkaline earth atoms (Li to K and Be to Ca) and a detailed analysis is performed for core polarization effects on ionization energies, electron affinities, oscillator strengths, polarizabilities, van der Waals coefficients, the valence electron density, and spin densities. Very accurate results are obtained for well-known energetic properties and spin densities at the nucleus. With respect to the other applications we consider our results as the most reliable to date with an estimated uncertainty of 1%–2%.

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