Dp. Chong, ACCURATE CALCULATION OF CORE-ELECTRON BINDING-ENERGIES BY THE DENSITY-FUNCTIONAL METHOD, Chemical physics letters, 232(5-6), 1995, pp. 486-490
Using a basis set of atomic natural orbitals of valence triple-zeta pl
us double polarization quality, the core-electron binding energies (CE
BEs) of HF, H2O, N-2 and CO were computed by the deMon density-functio
nal program with a combined functional of Becke's exchange (B88) with
Perdew's correlation (P86). Of four different versions of the transiti
on-state method tested, the unrestricted generalized transition-state
(uGTS) model showed most promise. Two other functionals were tested bu
t found to be inferior to the B88/P86 combination. The molecules HCN,
CO2 and H2CO were added in the comparative study of basis set converge
nce. The best procedure found (the uGTS model using B88/P86 functional
with Dunning's cc-pV5Z basis set) was applied to other molecules. The
average deviation from experiment for 20 computed CEBEs is 0.23 eV.