Table 4.
Assessment of computed Raman activities for different functionals vs. experimental results. The test set consistsa of N2, H2O, CH4, C2H2, C2H4, C2H6, NH3 and CH2F2. Mean error (ME), mean average error (MAE), and root mean square error (RMS) are all given in Å4 amu−1
| Basis set | Method | ME | MAE | RMS |
|---|---|---|---|---|
| 6-31G(d) | MP2b | −8.4 | 30.2 | 50.4 |
| M06-L | 1.0 | 33.0 | 50.2 | |
| HF | 0.9 | 30.2 | 49.2 | |
| LC-ωPBE | −6.5 | 29.4 | 48.9 | |
| M06-HF | −0.1 | 29.4 | 48.9 | |
| CAM-B3LYP | −4.0 | 29.5 | 48.7 | |
| B3LYP | −2.7 | 30.0 | 48.5 | |
| PBE | −2.3 | 30.5 | 48.1 | |
| HSE | −3.0 | 29.5 | 47.8 | |
| PBEh | −3.3 | 29.4 | 47.8 | |
| HCTH | −5.0 | 29.0 | 47.5 | |
| Sadlej pVTZ | PBE | 13.6 | 15.7 | 29.3 |
| HCTH | 13.0 | 15.1 | 28.8 | |
| B3LYP | 10.9 | 13.5 | 25.2 | |
| HF | 8.6 | 15.1 | 25.1 | |
| M06-L | 6.5 | 15.0 | 24.4 | |
| HSE | 9.1 | 12.3 | 23.1 | |
| PBEh | 8.7 | 12.2 | 22.7 | |
| M06-HF | 6.2 | 11.1 | 21.4 | |
| MP2b | 7.4 | 11.5 | 19.7 | |
| CAM-B3LYP | 7.0 | 10.9 | 17.6 | |
| LC-ωPBE | 1.7 | 11.2 | 17.4 | |
| aug-cc-pVTZ | PBE | 9.7 | 12.9 | 25.6 |
| HCTH | 8.1 | 12.4 | 24.0 | |
| HF | 5.9 | 14.6 | 23.7 | |
| B3LYP | 7.0 | 12.0 | 22.4 | |
| HSE | 5.9 | 11.7 | 21.1 | |
| PBEh | 5.7 | 11.7 | 20.9 | |
| CAM-B3LYP | 4.5 | 11.8 | 19.8 | |
| LC-ωPBE | −1.2 | 12.0 | 17.9 | |
| M06-L | 0.3 | 12.4 | 17.7 | |
| M06-HF | −2.7 | 11.6 | 17.3 | |
| MP2b | 2.3 | 10.0 | 16.7 |
a
Only those modes for which experimental activities were available were considered; modes that are inactive were not considered, and degenerate modes were considered only once.
b
From ref. 24.