Table 1.

MAD, (in kcal/mol) for various benchmarks

MethodsHOFIPEAPABDENHTBHHTBHNCIEAllTime*
(223)(38)(25)(8)(92)(38)(38)(31)(493)C100H202C100H100
DFT methods
SVWN (LDA)130.8815.1417.305.6818.1412.5317.953.2967.28
BLYP10.166.022.471.757.008.297.681.497.84
PBE20.715.132.401.563.918.579.481.1712.10
TPSS5.015.362.411.665.889.048.261.145.33
B3LYP6.083.742.451.405.514.844.260.984.982.812.3
B3LYP-D34.153.772.471.184.295.174.970.643.93
PBE05.643.842.971.253.673.564.380.714.36
M06-2X2.262.722.371.941.401.261.250.281.86
XYG31.811.311.841.611.571.290.750.321.51200.081.4
XYGJ-OS1.651.231.971.680.711.180.880.351.287.846.4
MC3BB3.282.784.011.032.431.440.800.582.58
B2PLYP2.742.482.151.522.952.231.730.552.45
B2PLYP-D1.672.482.151.342.272.472.110.451.88
ωB97X-2(LP)§1.521.731.561.091.621.670.740.471.44
Wavefunction based methods
HF213.4223.1926.463.0932.709.0813.512.37107.71
MP210.633.493.592.137.735.423.910.607.49
G21.890.971.311.341.800.971.240.571.56
G31.061.271.131.061.080.971.240.571.06

HOF is heat of formation (1, 2), IP is ionization potential (2), EA is electron affinity (2), PA is proton affinity (2), BDE is bond dissociation energy (40), NHTBH and HTBH are barrier heights for reactions (42, 43), NCIE is the binding in molecular clusters (42, 43). The basis sets used for final energetics are G3Large unless otherwise stated. See SI Text for computational details.

  • *The time is single CPU hours on 2.5 GHz Xeon for linear alkane C100H202 and the C100H100 diamond structure. The basis sets used are cc-pVDZ.

  • Taken from ref. 12 with 6-311+G(3df,2p).

  • HOF are taken from ref. 22 with very large basis set of CQZV3P. BDEs are calculated using the corresponding HOF.

  • §Taken from ref. 17 or calculated with 6-311++G(3df,3pd). BSSE corrections are included for the NCIE set.