Dependence of the calculated ionization potentials on correlation method relative to the spin-free experimental values. DKH/CBS(S4) values are shown throughout with only valence electron (4s4p) correlation.
The convergence with basis set of the DKH-CCSD(T) ionization potentials towards their CBS(S4) limits with only valence electrons (4s4p) correlated.
The deviation (in kcal mol−1) of the CCSD(T)/CBS(S4) ionization potentials with both the inclusion of scalar relativity and different correlation spaces relative to the spin-free experimental values.
The effects of higher order electron correlation on the calculated IPs. The Δ3d and Δ3s3p results refer to the core-valence correlation effects, i.e., IP(val + 3d) − IP(val) and IP(val + 3s3p3d) − IP(val + 3d), respectively.
Differences between PP-based and DKH-based CCSD(T) ionization potentials as a function of basis set for the case of 4s4p + 3s3p3d correlation.
Summary of the coupled cluster and basis set combinations used in the composite calculation of ionization potentials. a
Experimental ionization potentials (IPs) together with derived spin-free values. a
Contributions to the calculated ionization potentials (kcal mol−1) using coupled cluster methods with comparison of the final composite results with experiment.
Calculated differences between PP-CCSD(T) and DKH-CCSD(T) ionization potentials (in kcal mol−1).
Calculated differences between finite basis set CCSD(T)-F12b and conventional CCSD(T)/CBS(S4) ionization potentials (PP-based results, in kcal mol−1).
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