ACCURATE DENSITY-FUNCTIONAL CALCULATION OF CORE-ELECTRON BINDING-ENERGIES WITH A SCALED POLARIZED TRIPLE-ZETA BASIS-SET .3. EXTENSION TO OPEN-SHELL MOLECULES
Ch. Hu et Dp. Chong, ACCURATE DENSITY-FUNCTIONAL CALCULATION OF CORE-ELECTRON BINDING-ENERGIES WITH A SCALED POLARIZED TRIPLE-ZETA BASIS-SET .3. EXTENSION TO OPEN-SHELL MOLECULES, Chemical physics, 216(1-2), 1997, pp. 99-104
Density functional theory and the unrestricted generalized transition
state (uGTS) model were applied to study the core-electron binding ene
rgies (CEBEs) of open-shell molecules. Basis set scaling based on Clem
enti and Raimondi's rules for atomic screening was used along with the
cc-pVTZ basis set. The scaled pVTZ basis set is almost as good as the
cc-pV5Z and complete basis set limit in predicting CEBEs. For small m
olecules (O-2, NO, NF2 and NO2) the average absolute deviation (aad) o
f our prediction (scaled pVTZ) is only 0.29 eV. For the larger molecul
e (CF3)(2)NO the aad is 0.56 eV, compared with experimental uncertaint
y of 0.5 eV. Theoretical predicted multiplet splittings for the small
molecules agree quite well with experiment: the average deviation is -
0.33 eV. For (CF3)(2)NO the calculated multiplet splittings are much s
maller than the experimental ones. We also predict the CEBEs of PO, SN
and SO, which have not been observed experimentally. (C) 1997 Elsevie
r Science B.V.