Table 2.
Excitation energies of monocations (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. 4, taken from Ref. 38, T, W are the TZV and a modified spdf Wachters basis sets, respectively.
| Expt.a | Sc+ D(s1) → F(s0) 13.8 | Ti+ F(s1) → F(s0) 2.3 | V+ D(s0) → F(s1) 7.6 | Cr+ S(s0) → D(s1) 35.1 | Mn+ S(s1) → D(s0) 41.7 | Fe+ D(s1) → F(s0) 5.8 | Co+ F(s0) → F(s1) 9.9 | Ni+ D(s0) → F(s1) 24.9 | Cu+ D(s0) → D(s1) 64.8 | MAD | |
|---|---|---|---|---|---|---|---|---|---|---|---|
| Errors | CCSD(T) (T)b | 2.8 | 2.4 | −1.2 | 3.3 | 14.2 | 9.7 | −9.1 | −8.7 | 3.1 | 6.1 |
| QCISD(T) (W)c | 2.1 | 0.9 | 0.5 | 1.6 | 2.6 | −0.3 | 2.3 | 4.2 | 9.9 | 4.0 | |
| LACV3P** | −7.7 | −2.8 | −0.2 | 2.5 | −7.3 | −4.8 | 0.7 | −4.2 | −3.7 | 10.7 | |
| LACV3P++** | −7.7 | −2.6 | −0.3 | 2.4 | −7.7 | −4.9 | 1.5 | −3.2 | −2.3 | 10.6 | |
| QZVP(−g) | −9.9 | −7.7 | 5.4 | 3.3 | −13.6 | −10.4 | 7.0 | 3.4 | 0.7 | 7.0 | |