Accurate density-functional calculation of core-electron binding energies by a total-energy difference approach

A procedure for calculating core-electron binding energies (CEBEs), based o n a total-energy difference approach within Kohn-Sham density functional th eory, was investigated. Ten functional combinations and several basis sets (including unscaled, scaled, and core-valence correlated functions) were st udied using a database of reliable observed CEBEs. The functionals designed by Perdew and Wang (1986 exchange and 1991 correlation) were found to give the best performance with an average absolute deviation from experiment of 0.15 eV. The scaled basis sets did not perform satisfactorily, but it was found that the core-valence correlated cc-pCVTZ basis functions were an exc ellent alternative to the cc-pV5Z set as they provided equally accurate res ults and could be applied to larger molecules. (C) 1999 American Institute of Physics. [S0021-9606(99)30742-X].