TABLE 4.
Performance of a Range of DFT Methods for the Computation of Gas-Phase Homolytic P–F and P–Cl Bond Dissociation Energies (BDEs) in Conjunction with the A′VQZ basis set (in kJ mol−1).
| P–F BDEs | P–Cl BDEs | |||||||||
|---|---|---|---|---|---|---|---|---|---|---|
| Class | Functional | MAD | MD | LD | NO | MAD | MD | LD | NO | |
| GGA | revPBE | 25.8 | −25.8 | 37.9 (F30) | 29 | 23.3 | −23.3 | 29.0 (Cl1) | 29 | |
| revPBE-D3BJ | 20.4 | −20.4 | 33.1 (F30) | 28 | 8.8 | −8.8 | 13.6 (Cl29) | 11 | ||
| B97-D | 16.1 | −16.1 | 29.0 (F30) | 25 | 31.4 | −31.4 | 39.3 (Cl1) | 29 | ||
| HCTH407 | 13.3 | −13.3 | 22.3 (F30) | 22 | 26.4 | −26.4 | 32.9 (Cl1) | 29 | ||
| BLYP | 12.3 | −12.2 | 26.9 (F30) | 18 | 31.6 | −31.6 | 38.9 (Cl1) | 29 | ||
| BPW91 | 11.9 | −11.9 | 23.4 (F30) | 18 | 15.7 | −15.7 | 21.9 (Cl1) | 29 | ||
| BLYP-D3BJ | 8.4 | −7.7 | 23.0 (F30) | 10 | 17.4 | −17.4 | 23.5 (Cl1) | 29 | ||
| PBE-D3BJ | 6.2 | 4.8 | 15.1 (F1) | 5 | 4.6 | 4.4 | 8.5 (Cl14) | 0 | ||
| BP86-D3BJ | 5.2 | 2.3 | 13.5 (F1) | 3 | 3.5 | 2.5 | 7.6 (Cl8) | 0 | ||
| PBE | 5.1 | 2.6 | 12.7 (F1) | 4 | 3.0 | −1.8 | 8.1 (Cl1) | 0 | ||
| BP86 | 5.0 | −1.0 | 12.1 (F30) | 3 | 9.1 | −9.1 | 15.9 (Cl1) | 13 | ||
| MGGA | M11-L | 25.1 | −25.1 | 29.7 (F17) | 29 | 3.2 | −1.9 | 9.8 (Cl23) | 0 | |
| r 2SCAN | 14.9 | −14.9 | 21.6 (F2) | 27 | 9.7 | −9.7 | 16.9 (Cl1) | 12 | ||
| TPSS | 14.7 | −14.7 | 26.8 (F30) | 23 | 15.9 | −15.9 | 22.0 (Cl1) | 29 | ||
| TPSS-D3BJ | 12.0 | −12.0 | 24.6 (F30) | 18 | 7.6 | −7.6 | 12.9 (Cl1) | 8 | ||
| B97M-V | 10.9 | −10.9 | 18.8 (F2) | 12 | 2.9 | 0.2 | 8.2 (Cl1) | 0 | ||
| VSXC | 9.3 | −9.3 | 19.5 (F19) | 10 | 18.2 | −18.2 | 29.7 (Cl1) | 28 | ||
| τ-HCTH | 8.2 | −8.2 | 17.2 (F30) | 11 | 24.1 | −24.1 | 31.7 (Cl1) | 29 | ||
| MN12-L | 7.6 | −7.6 | 15.8 (F2) | 8 | 4.2 | 0.6 | 10.3 (Cl29) | 3 | ||
| MN15-L | 3.8 | −3.1 | 9.5 (F2) | 0 | 5.6 | 5.5 | 12.1 (Cl23) | 1 | ||
| HGGA | BH&HLYP | 49.0 | −49.0 | 54.8 (F30) | 29 | 42.9 | −42.9 | 47.6 (Cl1) | 29 | |
| SOGGA11-X | 23.0 | −23.0 | 27.7 (F30) | 29 | 11.0 | −11.0 | 15.1 (Cl1) | 16 | ||
| B3PW91 | 22.4 | −22.4 | 30.2 (F30) | 29 | 18.9 | −18.9 | 23.8 (Cl1) | 29 | ||
| APF | 22.0 | −22.0 | 28.8 (F30) | 29 | 14.7 | −14.7 | 19.4 (Cl1) | 29 | ||
| PBE0 | 21.7 | −21.7 | 27.9 (F30) | 29 | 11.8 | −11.8 | 16.3 (Cl1) | 22 | ||
| PBE0-D3BJ | 19.9 | −19.9 | 26.4 (F30) | 29 | 6.0 | −6.0 | 9.9 (Cl1) | 0 | ||
| B3LYP | 19.9 | −19.9 | 30.2 (F30) | 29 | 29.8 | −29.8 | 35.6 (Cl1) | 29 | ||
| B3PW91-D3BJ | 18.7 | −18.7 | 27.0 (F30) | 29 | 7.0 | −7.0 | 11.3 (Cl29) | 4 | ||
| APF-D | 18.5 | −18.5 | 24.8 (F30) | 29 | 10.6 | −10.6 | 15.2 (Cl1) | 16 | ||
| X3LYP | 18.4 | −18.4 | 28.3 (F30) | 28 | 27.8 | −27.8 | 33.5 (Cl1) | 29 | ||
| B3LYP-D3BJ | 16.2 | −16.2 | 27.1 (F30) | 27 | 18.0 | −18.0 | 23.0 (Cl29) | 29 | ||
| ωB97X-D | 14.2 | −14.2 | 22.4 (F30) | 27 | 11.2 | −11.2 | 15.3 (Cl21) | 20 | ||
| B971 | 12.0 | −12.0 | 20.2 (F30) | 20 | 8.6 | −8.6 | 14.9 (Cl1) | 14 | ||
| ωB97X | 10.2 | −10.2 | 18.5 (F30) | 15 | 12.8 | −12.8 | 16.2 (Cl29) | 27 | ||
| ωB97 | 7.6 | −7.6 | 17.3 (F30) | 6 | 15.5 | −15.5 | 20.2 (Cl29) | 29 | ||
| CAM-B3LYP | 7.3 | −7.3 | 16.8 (F30) | 8 | 27.3 | −27.3 | 31.4 (Cl21) | 29 | ||
| CAM-B3LYP-D3BJ | 5.8 | −5.7 | 15.5 (F30) | 3 | 21.5 | −21.5 | 26.4 (Cl29) | 29 | ||
| ωB97X-V | 4.1 | −4.0 | 13.0 (F30) | 2 | 5.6 | −5.6 | 10.1 (Cl30) | 1 | ||
| N12-SX | 3.2 | −0.6 | 8.0 (F2) | 0 | 4.7 | 4.4 | 11.8 (Cl14) | 2 | ||
| HMGGA | TPSSh | 23.2 | −23.2 | 33.4 (F30) | 29 | 18.8 | −18.8 | 24.1 (Cl1) | 29 | |
| PW6B95 | 9.2 | −9.2 | 16.4 (F30) | 13 | 8.3 | −8.3 | 14.0 (Cl12) | 11 | ||
| MN15 | 8.6 | 8.6 | 18.8 (F17) | 9 | 3.5 | −3.1 | 10.1 (Cl1) | 1 | ||
| PW6B95-D3BJ | 8.1 | −8.1 | 15.6 (F30) | 8 | 4.4 | −4.3 | 9.7 (Cl12) | 0 | ||
| τ-HCTHh | 8.0 | −8.0 | 16.6 (F30) | 10 | 11.9 | −11.9 | 19.0 (Cl1) | 18 | ||
| BMK | 5.8 | −5.8 | 10.7 (F30) | 3 | 2.3 | −0.6 | 6.3 (Cl14) | 0 | ||
| M06-2X | 4.6 | −4.6 | 7.5 (F2) | 0 | 4.8 | −4.8 | 8.1 (Cl1) | 0 | ||
| M08-HX | 3.8 | −3.7 | 8.8 (F30) | 0 | 6.8 | −6.8 | 10.5 (Cl29) | 1 | ||
| M06 | 3.7 | −3.4 | 10.3 (F19) | 1 | 3.8 | 3.1 | 7.8 (Cl14) | 0 | ||
| BMK-D3BJ | 3.6 | −3.5 | 8.7 (F30) | 0 | 10.0 | 10.0 | 15.0 (Cl8) | 14 | ||
| M05-2X | 3.0 | 2.6 | 7.2 (F9) | 0 | 6.0 | −6.0 | 10.7 (Cl21) | 1 | ||
| M11 | 3.0 | −1.9 | 8.5 (F30) | 0 | 12.9 | −12.9 | 18.7 (Cl29) | 24 | ||
| ωB97M-V | 2.2 | 1.4 | 5.5 (F6) | 0 | 2.4 | 2.3 | 4.8 (Cl14) | 0 | ||
| DHDFT | PBE0-DH | 23.5 | −23.5 | 26.7 (F30) | 29 | 9.7 | −9.7 | 11.6 (Cl1) | 15 | |
| PBE-QIDH | 12.1 | −12.1 | 14.2 (F30) | 27 | 2.3 | −2.1 | 4.0 (Cl29) | 0 | ||
| mPW2PLYP | 10.1 | −10.1 | 16.7 (F30) | 14 | 16.1 | −16.1 | 19.0 (Cl21) | 29 | ||
| B2PLYP | 8.8 | −8.8 | 16.1 (F30) | 10 | 16.3 | −16.3 | 19.4 (Cl21) | 29 | ||
| B2GP-PLYP | 7.4 | −7.4 | 13.1 (F30) | 4 | 12.6 | −12.6 | 15.8 (Cl29) | 25 | ||
| B2PLYP-D3BJ | 7.2 | −7.2 | 14.6 (F30) | 6 | 10.3 | −10.3 | 14.7 (Cl29) | 13 | ||
| B2K-PLYP | 6.1 | −6.1 | 11.0 (F30) | 1 | 10.3 | −10.3 | 13.5 (Cl29) | 21 | ||
| DSD-BLYP | 5.3 | 5.3 | 13.3 (F2) | 1 | 2.4 | −1.0 | 7.8 (Cl1) | 0 | ||
| DSD-PBEP86 | 5.2 | −5.0 | 9.9 (F30) | 0 | 2.4 | −0.9 | 7.8 (Cl1) | 0 | ||
| PWPB95 | 5.0 | −5.0 | 11.1 (F30) | 2 | 4.8 | −4.8 | 7.8 (Cl27) | 0 | ||
| DSD-PBEB95 | 2.1 | 1.7 | 6.7 (F2) | 0 | 2.2 | 2.1 | 7.9 (Cl1) | 0 | ||