Exploiting the Correlation between the 1s, 2s, and 2p Energies for the Prediction of Core-Level Binding Energies of Si, P, S, and Cl species.

The binding energies (BEs) of the 1s, 2s, and 2p core electrons of third-period elements (Si, P, S, Cl) were calculated using Hartree-Fock (HF) and B3LYP, BH&HLYP, and LC-BOP ΔSCF, and the shifted KS ΔSCF methods. Linear relationships between two BEs were derived and compared with the Auger parameter. The derived lines are essentially parallel, with only the intercepts differing. The difference in intercepts is due to the lack of electron correlation effects in HF and the self-interaction errors (SIEs) of the functional. The slope is the slope of the linear relationship between the chemical shifts. The straight lines between the 2s and 2p BEs also coincided with the Auger parameter lines, which have a slope of 1 by definition and an intercept being the difference between the 2s and 2p BEs. The shifted KS ΔSCF scheme compensates for SIEs, yielding equations that are approximately invariant. The calculated average gaps for the 2s and 2p BEs are 51.21 eV for Si, 57.48 eV for P, 63.85 eV for S, and 70.48 eV for Cl. The straight lines representing the relationships between the BEs of the 1s and 2s and 1s and 2p electrons are also parallel to each other in ΔSCF and converge into a single line in the shifted ΔSCF scheme. However, these lines are steeper than the Auger parameter line. The derived relationships can be used to predict unknown BEs, which we have applied to many molecules. The results are highly accurate, with mean absolute errors (MAEs) of less than 0.2 eV compared to experimental values.