Table 1. Error Statistics (kcal/mol) for the GMTKN55 Database and Its Five Top-Level Subsets of Selected WFT, cWFT, and DFT Methodsa.
methods | WTMAD2 | thermo | barrier | large | confor. | intermol. |
---|---|---|---|---|---|---|
cWFT | ||||||
G4(MP2)-XK-T | 1.43 | 0.40 | 0.18 | 0.18 | 0.11 | 0.56 |
G4-Q-DLPNO | 1.52 | 0.25 | 0.12 | 0.20 | 0.46 | 0.49 |
G4-T | 1.51 | 0.35 | 0.16 | 0.23 | 0.14 | 0.63 |
G4-T-DLPNO | 1.66 | 0.26 | 0.12 | 0.24 | 0.52 | 0.52 |
G4(MP3)-D | 1.65 | 0.37 | 0.17 | 0.28 | 0.30 | 0.55 |
G4(MP3|KS)-D | 1.96 | 0.41 | 0.28 | 0.26 | 0.45 | 0.56 |
G4(MP2)-XK-D | 2.56 | 0.46 | 0.29 | 0.34 | 0.68 | 0.79 |
G44 | 2.52 | 0.38 | 0.23 | 0.75 | 0.38 | 0.78 |
G4(MP2)5 | 2.96 | 0.53 | 0.34 | 0.91 | 0.33 | 0.85 |
CBS-QB310,11 | 3.10 | 0.40 | 0.35 | 0.60 | 0.20 | 1.55 |
rev-G4MP2XK | 3.53 | 0.50 | 0.29 | 0.61 | 1.16 | 0.96 |
MP2.X-Q | 3.29 | 0.71 | 0.78 | 0.88 | 0.42 | 0.50 |
G4(MP2)-XK53 | 3.71 | 0.45 | 0.31 | 0.67 | 1.25 | 1.02 |
WFT | ||||||
SCS-MP2-D389,b | 5.22 | 1.23 | 0.95 | 1.39 | 0.91 | 0.75 |
SCS-MP289 | 5.35 | 0.94 | 1.01 | 1.15 | 1.02 | 1.23 |
MP2-D3b | 5.83 | 1.21 | 1.21 | 1.66 | 0.87 | 0.87 |
MP2-D3c | 5.54 | 1.20 | 1.18 | 1.52 | 0.80 | 0.84 |
MP2 | 6.91 | 1.21 | 1.23 | 1.78 | 1.47 | 1.21 |
HF-D3d | 13.08 | 5.05 | 2.65 | 2.06 | 1.85 | 1.48 |
HF | 29.46 | 5.87 | 3.74 | 3.66 | 7.27 | 8.92 |
DFT | ||||||
ωB97M(2)49 | 2.19 | 0.44 | 0.26 | 0.42 | 0.58 | 0.49 |
xrevDSD-PBEP86-D445 | 2.26 | 0.56 | 0.27 | 0.52 | 0.43 | 0.47 |
revDSD-PBEP86-D445 | 2.33 | 0.56 | 0.31 | 0.58 | 0.41 | 0.48 |
revDOD-PBEP86-D445 | 2.36 | 0.59 | 0.30 | 0.59 | 0.41 | 0.47 |
revDSD-PBEP86-NL | 2.44 | 0.55 | 0.30 | 0.55 | 0.47 | 0.57 |
revDSD-PBE-D445 | 2.46 | 0.65 | 0.35 | 0.53 | 0.43 | 0.50 |
revDSD-PBEP86-D345 | 2.42 | 0.54 | 0.31 | 0.55 | 0.46 | 0.57 |
revDSD-BLYP-D445 | 2.59 | 0.57 | 0.34 | 0.58 | 0.48 | 0.62 |
DSD-SCAN-D445 | 2.64 | 0.60 | 0.40 | 0.62 | 0.45 | 0.56 |
DSD-PBE-D442 | 2.64 | 0.61 | 0.39 | 0.56 | 0.53 | 0.54 |
DSD-PBEP86-D442 | 2.65 | 0.54 | 0.37 | 0.63 | 0.55 | 0.56 |
revDSD-PBEB95-D445 | 2.70 | 0.64 | 0.31 | 0.45 | 0.78 | 0.52 |
DSD-BLYP-D445 | 2.83 | 0.58 | 0.38 | 0.59 | 0.68 | 0.60 |
DSD-PBEP86-D342 | 3.10 | 0.55 | 0.45 | 0.49 | 0.65 | 0.97 |
DSD-PBE-D342 | 3.17 | 0.66 | 0.41 | 0.54 | 0.73 | 0.83 |
B2GP-PLYP-D390 | 3.19 | 0.63 | 0.42 | 0.66 | 0.64 | 0.85 |
ωB97M-V91 | 3.29 | 0.73 | 0.45 | 0.64 | 0.90 | 0.57 |
ωB97X-V92 | 3.96 | 1.02 | 0.56 | 1.07 | 0.73 | 0.58 |
M06-2X-D3(0)93 | 4.79 | 0.86 | 0.48 | 1.08 | 1.22 | 1.14 |
B3LYP-D3 | 6.50 | 1.31 | 1.14 | 1.66 | 1.15 | 1.24 |
D3 stands for D3(BJ) throughout this table; M06-2X was evaluated with a D3(0) correction, for want of D3BJ parameters. Statistics for M06-2X without D3(0) are essentially identical. Tabulated data for the DFT methods employing the def2-QZVPP basis set (def2-QZVPPD for subsets AHB21, G21EA, IL16, RG18, and WATER27) were obtained from refs (45 and 46) while the WFT (MP2, SCS-MP2, and HF) data in the same basis sets were obtained in this work, as were all cWFT results. The abbreviations “thermo”, “barrier”, “large”, “confor.”, and ‘intermol.’ stand for basic thermochemistry, barrier heights, reactions involving large molecules, conformer energies, and intermolecular interactions, respectively.
D3(BJ) parameters taken from Table S1 of ref (94).
a1 = 0, a2 = 5.5, s6 = −0.345, s8 = 0 (this work).
Present work; D3(BJ) parameters from Table 2 of the original D3(BJ) paper.70