Table 1.
Excitation energies of atoms (kcal∕mol) from experiment, errors (kcal∕mol) against experiment (theory-experiment) obtained by other authors with high level ab initio methods and the errors obtained with B3LYP for our different basis sets. Experimental values quoted in Ref. 6, taken from Ref. 36. The QCISD(T) calculations have been done with a modified basis set based on Wachters.
| Expt.a | Sc D(s2) → F(s1) 33.0 | Ti F(s2) → F(s1) 18.7 | V F(s2) → D(s1) 5.8 | Cr D(s2) → D(s1) −23.1 | Mn S(s2) → D(s1) 49.6 | Fe D(s2) → F(s1) 20.1 | Co F(s2) → F(s1) 9.7 | Ni F(s2) → D(s1) −0.7 | Cu D(s2) → S(s1) −34.4 | MAD | |
|---|---|---|---|---|---|---|---|---|---|---|---|
| Errors | QCISD(T)b | 1.4 | 0 | −0.9 | −2.3 | 2.1 | −0.2 | −2.1 | −3.5 | −8.3 | 2.3 |
| LACV3P** | −14.4 | −9.4 | −5.1 | −6.2 | −8.8 | −7 | −2.4 | 2.3 | 1.6 | 6.4 | |
| LACV3P++** | −14.6 | −10 | −6.7 | −8.1 | −12.9 | −9.8 | −6.7 | −2.2 | −3.6 | 8.3 | |
| QZVP(−g) | −16.2 | −13.9 | −11 | −8.8 | −17.1 | −14.8 | −12.1 | −8.7 | −7.1 | 12.2 | |