The verification of delta SCF and Slater's transition state theory for the calculation of core ionization energy

Abstract

AbstractThe core ionization energies of second‐ and third‐period elements of the molecules C2H5NO2, SiF4, Si(CH3)4, PF3, POF3, PSF3, CS2, OCS, SO2, SO2F2, CH3Cl, CFCl3, SF5Cl, and Cl3PS are calculated by using Hartree‐Fock (HF), and Kohn‐Sham (KS) with BH&HLYP, B3LYP, and LC‐BOP functionals. We used ΔSCF, Slater's transition state (STS), and two previously proposed shifted STS (1) and shifted STS (2) methods, which have been developed. The errors of ΔSCF and STS come mainly from the self‐interaction errors (SIE) and can be corrected with a shifting scheme. In this study, we used the shifting parameters determined for each atom. The shifted STS (1) reproduces ΔSCF almost perfectly with mean absolute deviations (MAD) of 0.02 eV. While ΔSCF and STS vary significantly depending on the functional used, the variation of shifted STS (2) is small, and all shifted STS (2) values are close to the observed ones. The deviations of the shifted STS (2) from the experiment are 0.24 eV (BH&HLYP), 0.19 eV (B3LYP), and 0.23 eV (LC‐BOP). These results further support the use of shifted STS methods for predicting the core ionization energies.