Table 2. Calculated relative energies (kcal mol–1), geometries (bond lengths in Å, bond angles in degrees), vibrational frequencies (unscaled, cm–1) and intensities (km mol–1) of the neutral NPrO molecule at the B3LYP, CCSD(T) and CASPT2 levels of theory.
|
|
B3LYP |
CCSD(T) |
CASPT2 |
||||||
| Pr(v) | Pr(iv) | Pr(iii) | Pr(v) | Pr(iv) | Pr(iii) | Pr(v) | Pr(iv) | ||
| ΔE | 0.0 | –7.5 | 54.7 | 0 | 10.8 | 43.4 | |||
| State | 1Σ– | 3Φ | 5A′ | 1Σ– | 3Φ | 5A′ | 1Σ– | 3Φ | |
| Electron configuration | f0σ2π4 | fφ1σ1π4 | f2σ1π3 | f0σ2π4 | fφ1σ1π4 | f2σ1π3 | f0σ2π4 | fφ1σ1π4 | |
| Pr–O | 1.765 | 1.805 | 1.829 | 1.775 | 1.810 | 1.828 | 1.794 | 1.811 | |
| Pr–N | 1.677 | 1.767 | 2.361 | 1.697 | 1.779 | 2.242 | 1.723 | 1.769 | |
| ∠OPrN | 180.0 | 180.0 | 127.4 | 180.0 | 180.0 | 117.1 | 180.0 | 180.0 | |
| ν | Pr–N stretch | 1021.1(378) | 826.8(284) | 330.5(73) | 960 | 819.3 | 402.1 | 896.8(401) | 818.4(231) |
| Pr–O stretch | 822.1(194) | 736.2(59) | 784.6(300) | 788.6 | 723.1 | 776.9 | 735.6(97) | 784.1(64) | |
| NPrO bend | 157.0(78) | 168.4(74) | 63.4(54) | 125.7 | 164.9 | 119.6 | |||
| S 2 | 0.0 | 2.01 | 6.02 | ||||||
| T 1 | 0.056 | 0.046 | 0.032 | ||||||
| D 1 | 0.167 | 0.123 | 0.091 | ||||||