Key geometrical parameters (Å) for the various spin states of [(TPFC)Mn(O2)] complex and energies (kcal mol−1) relative to the separated [(TPFC)Mn] (S = 2) and O2 (S = 1).
| d(Mn–O) | d(O–O) | ΔG (ΔH) | |||||||
|---|---|---|---|---|---|---|---|---|---|
| BP86 | TPSSh | B3LYP | BP86 | TPSSh | B3LYP | BP86-D3 | TPSSh-D3 | B3LYP-D3 | |
| Septet | 3.63 | 3.64 | 3.64 | 1.22 | 1.20 | 1.20 | −0.5 (−7.2) | 3.8 (−1.7) | 5.7 (−1.8) |
| Quintet | 2.01 | 2.16 | 2.12 | 1.27 | 1.24 | 1.21 | −2.3 (−11.4) | 12.6 (5.1) | 16.9 (9.5) |
| Triplet | 1.88 | 2.27 | 2.77 | 1.26 | 1.22 | 1.20 | −9.3 (−20.0) | 7.5 (−1.2) | 7.2 (0.2) |
| Singlet | 1.64 | 1.80 | 1.81 | 1.25 | 1.25 | 1.27 | −1.9 (−13.4) | 26.8 (16.9) | 33.7 (22.6) |