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. 2022 Jul 21;24(30):18028–18042. doi: 10.1039/d2cp02234f

Reaction barriers (ΔE‡) and energies (ΔErxn) (kcal mol−1) for the pericyclic systems of Scheme 1, computed using various density functional approximations at the XC/QZ4P//CCSD(T)/cc-pVTZ level.

XC Diels-Alder reaction 1,3-Dipolar cycloaddition Electrocyclic rearrangement Sigmatropic rearrangement Double group transfer
ΔE‡ ΔErxn ΔE‡ ΔErxn ΔE‡ ΔErxn ΔE‡ ΔErxn ΔE‡ ΔErxn
LDA
VWN −0.5 −65.4 2.5 −42.3 36.3 2.4 21.7 0.0 21.9 0.0
GGAs
BP86 14.7 −42.3 15.6 −20.4 39.5 8.2 28.1 0.0 38.1 0.0
BLYP 21.3 −30.1 19.8 −10.6 42.6 13.7 31.7 0.0 45.3 0.0
BEE 15.7 −43.1 17.4 −19.6 38.8 6.2 27.9 0.0 38.4 0.0
PW91 12.0 −46.3 13.4 −23.8 39.2 7.3 27.6 0.0 35.7 0.0
PBE 12.4 −46.4 14.0 −23.4 38.9 6.6 27.4 0.0 35.8 0.0
PBEsol 5.8 −57.0 8.5 −33.5 36.6 3.2 23.8 0.0 28.3 0.0
RPBE 18.7 −38.1 19.5 −15.3 39.8 8.1 29.7 0.0 41.7 0.0
revPBE 18.3 −38.9 19.4 −15.9 39.6 7.7 29.3 0.0 41.2 0.0
mPBE 14.1 −44.1 15.5 −21.2 39.2 7.1 28.1 0.0 37.4 0.0
mPW 15.2 −41.9 16.3 −19.4 39.8 8.2 28.7 0.0 38.9 0.0
HTBS 13.2 −47.2 15.5 −23.7 37.4 4.6 25.9 0.0 35.5 0.0
OLYP 23.8 −36.1 24.3 −13.2 40.3 7.0 30.6 0.0 45.3 0.0
OPBE 18.5 −48.7 22.0 −22.1 36.6 −0.1 26.7 0.0 38.8 0.0
XLYP 21.7 −28.9 19.9 −9.7 43.0 14.5 32.4 0.0 46.1 0.0
Meta-GGAs
M06-L 17.2 −46.2 20.7 −16.9 43.6 5.9 33.9 0.0 45.9 0.0
MVS 12.2 −54.5 18.5 −24.8 42.7 5.9 28.2 0.0 36.6 0.0
TPSS 15.4 −40.3 16.2 −19.5 40.1 7.7 30.8 0.0 43.0 0.0
revTPSS 14.4 −42.4 15.2 −22.7 39.6 6.1 31.4 0.0 44.9 0.0
Hybrids
B3LYP 22.8 −37.6 22.0 −18.6 44.8 11.7 35.0 0.0 49.6 0.0
B3LYP* 20.8 −38.3 20.1 −19.0 43.7 11.4 33.4 0.0 46.7 0.0
B1LYP 24.3 −37.3 23.3 −19.0 45.6 12.0 36.4 0.0 52.0 0.0
B1PW91 19.3 −48.7 21.2 −26.7 42.4 5.7 33.0 0.0 46.1 0.0
BHandH 12.3 −66.7 14.2 −48.4 44.2 3.6 34.1 0.0 42.4 0.0
BHandHLYP 27.2 −44.6 26.6 −27.8 48.6 10.3 41.2 0.0 58.5 0.0
KMLYP 19.0 −60.5 20.5 −42.4 46.5 5.1 38.0 0.0 50.1 0.0
O3LYP −3.3 −76.1 0.4 −53.5 37.3 0.2 22.7 0.0 21.5 0.0
OPBE0 20.5 −54.6 24.2 −29.8 40.0 −0.3 31.5 0.0 45.1 0.0
PBE0 16.1 −52.8 18.2 −30.8 41.8 4.8 32.1 0.0 42.9 0.0
mPW1PW 18.4 −49.1 20.1 −27.5 42.6 6.2 33.2 0.0 45.6 0.0
mPW1K 20.6 −54.2 22.7 −33.6 44.6 4.7 36.5 0.0 50.2 0.0
S12H 16.2 −53.4 19.3 −29.1 42.7 4.5 34.0 0.0 44.0 0.0
X3LYP 22.0 −39.2 21.3 −20.5 44.8 11.5 35.1 0.0 49.2 0.0
Meta-hybrids
M06 19.5 −47.9 22.7 −22.7 43.5 7.0 34.9 0.0 48.4 0.0
M06-2X 17.8 −48.8 20.7 −29.7 44.5 7.9 36.6 0.0 49.0 0.0
M06-HF 13.8 −48.4 17.1 −40.7 42.9 9.5 37.7 0.0 50.7 0.0
TPSSH 16.7 −43.3 17.8 −22.6 41.2 6.8 32.4 0.0 45.2 0.0
Double-hybrids
B2K-PLYP 16.0 −49.2 17.6 −25.8 44.1 8.5 37.4 0.0 49.2 0.0
B2T-PLYP 17.7 −45.6 18.5 −23.2 44.1 9.5 36.7 0.0 49.2 0.0
B2-PLYP 17.9 −43.9 18.4 −21.2 43.7 10.0 35.9 0.0 48.5 0.0
LS1-TPSS 10.6 −56.7 14.4 −30.3 41.9 4.8 36.3 0.0 45.6 0.0
mPW2K-PLYP 15.7 −49.4 17.2 −26.1 44.1 8.7 37.5 0.0 49.1 0.0
mPW2-PLYP 18.4 −44.8 18.8 −23.1 44.6 10.2 36.9 0.0 49.6 0.0
PBE0-DH 15.9 −56.8 18.7 −33.8 42.8 4.0 34.8 0.0 45.9 0.0
revDSD-BLYP 15.2 −49.3 16.8 −25.8 44.3 9.0 38.3 0.0 49.7 0.0
revDSD-PBE 14.5 −52.1 16.8 −27.4 43.1 6.7 37.3 0.0 47.8 0.0
revDSD-PBEP86 16.8 −49.4 18.6 −25.2 43.9 7.6 38.4 0.0 50.0 0.0
Range-separated hybrids
CAM-B3LYP 23.7 −45.4 22.1 −27.8 46.0 9.2 37.3 0.0 51.7 0.0
CAMY-B3LYP 21.7 −44.5 20.7 −26.3 45.3 9.9 36.1 0.0 49.7 0.0
ωB97 23.7 −56.1 22.6 −35.2 46.5 3.2 40.4 0.0 53.0 0.0
ωB97X 23.0 −52.3 22.2 −32.3 46.0 5.4 38.8 0.0 51.7 0.0
ωB97X-D 23.1 −47.7 23.0 −27.9 44.7 6.3 36.4 0.0 50.2 0.0
Dispersion-corrected
BP86-D3(BJ) 8.4 −47.2 11.2 −24.4 39.3 8.4 27.6 0.0 34.7 0.0
BLYP-D3(BJ) 13.2 −36.5 14.1 −15.9 42.2 13.8 31.0 0.0 41.0 0.0
PBE-D3(BJ) 8.4 −49.5 11.1 −26.0 38.7 6.7 27.1 0.0 33.5 0.0
OLYP-D3(BJ) 6.8 −50.5 11.9 −25.8 38.9 6.8 27.4 0.0 36.1 0.0
OPBE-D3(BJ) 1.7 −62.6 9.9 −34.1 35.4 −0.1 24.0 0.0 29.7 0.0
B3LYP-D3(BJ) 16.2 −42.8 17.3 −22.9 44.4 11.8 34.4 0.0 46.0 0.0
PBE0-D3(BJ) 12.6 −55.5 15.7 −33.1 41.7 4.9 31.8 0.0 40.9 0.0
M06-2X-D3 17.6 −48.9 20.6 −29.7 44.5 7.9 36.6 0.0 48.9 0.0