Density-functional calculation of core-electron binding energies of C, N, O, and F

Abstract

The unrestricted generalized transition-state model using B88/P86 functional with Dunning’s cc-pV5Z basis set, found to be an excellent method of calculating core-electron binding energies (CEBEs), was further applied to many more molecules, some of which contain atoms from the third period. Estimation of relativistic corrections has also been refined. The average absolute deviation of over 50 calculated CEBEs from experiment is 0.30 eV before inclusion of approximate relativistic corrections (Crel), and 0.23 eV after adding Crel. Those molecules with observed CEBEs served to confirm our procedure, whereas the other cases provided our prediction of CEBEs.