Table 4 Relative energies (kcal mol−1) of the singlet and triplet electronic states of Co(L)(Cor) (L = O2, N2, CO, OC) with respect to their corresponding ground state.
From: Selectivity of Cobalt Corrole for CO vs. O2 and N2 in Indoor Pollution
State | Configuration | O2 | N2 | CO | OC |
|---|---|---|---|---|---|
BP86/def2-TZVP | |||||
Singlet | \(({{\rm{d}}}_{{{\rm{x}}}^{2}-{{\rm{y}}}^{2}})\) 2 \(({{\rm{d}}}_{{\rm{xz}}})\) 2 \(({{\rm{d}}}_{{\rm{yz}}})\) 2 \(({{\rm{d}}}_{{{\rm{z}}}^{2}})\) 0 \({({\rm{Cor}})}^{2}\) | 1.1 | 0.0 | 0.0 | 0.0 |
Triplet | \(({{\rm{d}}}_{{{\rm{x}}}^{2}-{{\rm{y}}}^{2}})\) 2 \(({{\rm{d}}}_{{\rm{xz}}})\) 2 \(({{\rm{d}}}_{{\rm{yz}}})\) 2 \(({{\rm{d}}}_{{{\rm{z}}}^{2}})\) ↑ \({({\rm{Cor}})}^{\uparrow }\) | 0.0 | 6.3 | 17.5 | NP |
B3LYP-D3/def2-TZVP | |||||
Singlet (BS) | \(({{\rm{d}}}_{{{\rm{x}}}^{2}-{{\rm{y}}}^{2}})\) 2 \(({{\rm{d}}}_{{\rm{xz}}})\) 2 \(({{\rm{d}}}_{{\rm{yz}}})\) 2 \(({{\rm{d}}}_{{{\rm{z}}}^{2}})\) ↑ \({({\rm{Cor}})}^{\downarrow }\) | 8.2 (6.4) | 0.0 (0.0) | 0.0 (0.0) | 0.0 (0.0) |
Singlet | \(({{\rm{d}}}_{{{\rm{x}}}^{2}-{{\rm{y}}}^{2}})\) 2 \(({{\rm{d}}}_{{\rm{xz}}})\) 2 \(({{\rm{d}}}_{{\rm{yz}}})\) 2 \(({{\rm{d}}}_{{{\rm{z}}}^{2}})\) 0 \({({\rm{Cor}})}^{2}\) | 25.2 (25.2) | 13.2 (4.7) | 2.4 (0.2) | 18.3 (12.1) |
Triplet | \(({{\rm{d}}}_{{{\rm{x}}}^{2}-{{\rm{y}}}^{2}})\) 2 \(({{\rm{d}}}_{{\rm{xz}}})\) 2 \(({{\rm{d}}}_{{\rm{yz}}})\) 2 \(({{\rm{d}}}_{{{\rm{z}}}^{2}})\) ↑ \({({\rm{Cor}})}^{\uparrow }\) | 0.0 (0.0) | 6.5 (−2.0) | 9.8 (7.6) | NP |
