Electron cross relaxation as a function of single relaxation contributions in double‐core ionization energies and spin–orbit splitting of atoms from Ar to Ba. I. 1s−2p− double‐core holes

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AbstractOn the basis of numerical ab initio, delta and multiconfiguration Breit–Dirac–Fock (ΔBDF and MCBDF) computations, we have investigated the dependence of electron “cross relaxation” on the single relaxation contributions in double‐core ionization energies and spin–orbit splitting of atoms from Ar to Ba, excluding transition elements. The cross‐relaxation variation with Z was fitted to a quadratic function of the geometric average of the single relaxation contributions. For the family of atoms AlCl, it was found that the splitting of the levels is not a straight measure of 2p spin–orbit coupling. The families of “light” atoms ArCa and CuSr yielded together a set of best‐fit coefficients, while the family of heavier atoms AgBa yielded another set. The best‐fit functions were used to predict double‐core ionization energies from single ionization data and from Koopmans' values for atoms from Ar to Ba. For molecules a semiempirical expression is proposed. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007