Table 1.

MAD, (in kcal/mol) for various benchmarks

Methods	HOF	IP	EA	PA	BDE	NHTBH	HTBH	NCIE	All	Time*
	(223)	(38)	(25)	(8)	(92)	(38)	(38)	(31)	(493)	C100H202	C100H100
DFT methods
SVWN (LDA)	130.88	15.14	17.30	5.68	18.14	12.53	17.95	3.29	67.28
BLYP	10.16	6.02	2.47	1.75	7.00	8.29	7.68	1.49	7.84
PBE	20.71	5.13	2.40	1.56	3.91	8.57	9.48	1.17	12.10
TPSS	5.01	5.36	2.41	1.66	5.88	9.04	8.26	1.14	5.33
B3LYP	6.08	3.74	2.45	1.40	5.51	4.84	4.26	0.98	4.98	2.8	12.3
B3LYP-D3	4.15	3.77	2.47	1.18	4.29	5.17	4.97	0.64	3.93
PBE0	5.64	3.84	2.97	1.25	3.67	3.56	4.38	0.71	4.36
M06-2X	2.26	2.72	2.37	1.94	1.40	1.26	1.25	0.28	1.86
XYG3†	1.81	1.31	1.84	1.61	1.57	1.29	0.75	0.32	1.51	200.0	81.4
XYGJ-OS	1.65	1.23	1.97	1.68	0.71	1.18	0.88	0.35	1.28	7.8	46.4
MC3BB	3.28	2.78	4.01	1.03	2.43	1.44	0.80	0.58	2.58
B2PLYP‡	2.74	2.48	2.15	1.52	2.95	2.23	1.73	0.55	2.45
B2PLYP-D‡	1.67	2.48	2.15	1.34	2.27	2.47	2.11	0.45	1.88
ωB97X-2(LP)§	1.52	1.73	1.56	1.09	1.62	1.67	0.74	0.47	1.44
Wavefunction based methods
HF	213.42	23.19	26.46	3.09	32.70	9.08	13.51	2.37	107.71
MP2	10.63	3.49	3.59	2.13	7.73	5.42	3.91	0.60	7.49
G2	1.89	0.97	1.31	1.34	1.80	0.97	1.24	0.57	1.56
G3	1.06	1.27	1.13	1.06	1.08	0.97	1.24	0.57	1.06

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.