Deviations of the reaction energies of the MP2, OO-RI-MP2, and OB-MP2 methods with the cc-pVDZ (upper panel) and cc-pVTZ (lower panel) basis sets from the CCSD(T) reference data.
Errors of the reaction energies of the OB-MP2-F12 method with the cc-pVDZ and cc-pVTZ basis sets in comparison with the CCSD(T)/cc-pVQZ values.
Reference IPs versus minus HOMO energies (−εHOMO) from HF, B3LYP, LC-wPBE, and OB-MP2 calculations as well as [Eq. (22a) ] for alkali metals (upper panel) and non-metallic molecules (lower panel). The straight line represents perfect correlation of measurements. The values in the parentheses inside the plots are the experimental IPs in units of eV (see Table IV for details).
Reference EAs versus minus LUMO energies (−εLUMO) from HF, B3LYP, LC-wPBE, and OB-MP2 calculations as well as [Eq. (22b) ] for alkali metals (upper panel) and non-metallic molecules excluding Ar and Ne gases (lower panel). The straight line represents perfect correlation of measurements. The values in the parentheses inside the plots are the experimental or vertical CCSD(T) EAs in units of eV (see Table IV for details).
Energy levels of the valence orbital states (1a g , 1e g , t 2g , t 1u , 2e g , and 2a g ) of in the closed-shell singlet state 1Σ with various bond lengths: R(Fe–H) = 1.35, 1.40, 1.45, and 1.50 Å, calculated by the (a) HF, (b) PBE, and (c) OB-MP2 methods. (d) The 3D plots of the MOs from the OB-MP2 calculation. The bonding 1a 1g and 1e g orbitals and the nonbonding t 2g (d xy , d yz , d zx ) orbitals are doubly-occupied. The bonding t 1u and anti-bonding 2e g and 2a 1g orbitals are empty states.
The 3D plots of the 2π(d zx , d yz , π*(NO)), , and orbitals of the CoNO molecule. They are doubly-occupied in the HF, B3LYP, and OB-MP2 calculations. Co, N, and O atoms are shown in purple, blue, and red, respectively.
Benchmark set of 25 reactions.
Statistical deviations of MP2, OO-RI-MP2, and OB-MP2 reaction energies from CCSD(T) reference data with the cc-pVDZ and cc-pVTZ basis sets. Maximum absolute deviation (MAX), difference between maximum and minimum absolute deviations ( ), root mean square (RMS), and mean absolute deviation (MAD) are shown in E h .
Statistical performance (in E h ) against the reaction energies calculated with CCSD(T)/cc-pVQZ for the reaction set in Table I .
Test molecules and reference IP and EA values (in eV) used for benchmark calculations. The experimental values are taken from Ref. 146 . The values obtained at the CCSD(T)/cc-pVTZ level of theory are used for reference where experimental data are not available.
Orbital energies (in E h ) of the occupied orbital states 2π(d zx , d yz , π*(NO)), and (shown in Fig. 6 ) of CoNO from the HF, B3LYP, and OB-MP2 calculations.
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