Why the Standard B3LYP/6-31G∗ Model Chemistry

Should Not Be Used in DFT Calculations of

Molecular Thermochemistry - Understanding and

Correction of the Problem

Supporting Information

Holger Kruse,† Lars Goerigk,‡ and Stefan Grimme∗,¶

Theoretische Organische Chemie, Organisch-Chemisches Institut der Universität Münster,

Corrensstraße 40, D-48149 Münster, Germany, School of Chemistry, The University of Sydney,

Sydney, New South Wales 2006, Australia, and Mulliken Center for Theoretical Chemistry, Institut
für Physikalische und Theoretische Chemie der Universität Bonn Beringstr. 4, D-53115 Bonn,
Germany.

E-mail: grimme@thch.uni-bonn.de

∗ Towhom correspondence should be addressed

† University of Münster
‡ The University of Sydney
¶ University of Bonn

1
Contents

1 definition of frozen coordinates for figure 1 3

2 numerical values for figures 2, 3, 4 4

3 molecular structure data for the fullerene mediated reactions 7

4 single point energies for the applications section 13

2
1 definition of frozen coordinates for figure 1

Figure S1: Starting structure of the potential energy surface scan (transition state). The frozen
coordinates are depicted as dashed lines. The initial bond length value for the two to-be-formed
C-C bond is 2.2 Å. To inhibit tilting of both reactants towards each other the C-N distances at
the opposite site are also frozen, they have an initial value of 3.2 Å. Both distances are changes
simultaneously as described in the manuscript.

3
2 numerical values for figures 2, 3, 4

Table S1: Mean deviations (MDs) for 26 sets of the GMTKN30 benchmark suit in kcal/mol. The
basis set 6-31G∗ is used for all calculations

GMTKN30 set B3LYP B3LYP-D3 B3LYP-gCP-D3

MB08-165 -15.77 -11.07 -12.45
W4-08 -7.39 -5.89 -9.42
G21IP -2.16 -2.16 -2.21
PA 2.85 3.32 1.11
SIE11 7.21 8.46 7.15
BHPERI 1.99 -2.59 -0.54
BH76 -6.34 -7.13 -5.67
BH76RC 0.74 0.73 0.16
RSE43 2.86 2.62 2.94
O3ADD6 -0.11 0.27 -0.74
G2RC -1.75 -1.24 -3.28
AL2X -5.13 1.20 -4.12
NBPRC -0.5 2.41 2.06
ISO34 -1.32 -1.00 -1.16
ISOL22 -4.5 -2.62 -4.27
DC9 -7.76 -3.49 -5.09
DARC -6.65 1.08 -3.69
ALK6 -8.42 -0.48 -0.6
BSR36 -11.86 -4.51 -5.66
IDISP -2.82 -0.63 -2.00
S22 -1.53 2.55 2.55
ADIM6 -4.24 0.91 0.91
PCONF -2.21 1.21 1.21
ACONF 0.81 -0.16 -0.16
SCONF 1.01 1.27 1.27
CYCONF 0.24 0.78 0.78

4
Table S2: Mean absolute deviation differences (∆MAD) to the B3LYP-D3/def2-QZVP reference
(ref) in kcal/mol for B3LYP/6-31G∗ and B3LYP-gCP-D3/6-31G∗ (method).

GMTKN30 set B3LYP/6-31G∗ B3LYP-gCP-D3/6-31G∗

MB08-165 10.60 8.48
W4-08 4.58 6.07
G21IP 0.96 1.02
PA 3.57 3.06
SIE11 1.07 0.98
BHPERI 0.66 −0.48
BH76 1.86 1.08
BH76RC 6.20 6.00
RSE43 0.74 0.82
O3ADD6 2.74 1.73
G2RC 7.07 8.44
AL2X 6.14 2.51
NBPRC 1.26 1.65
ISO34 1.10 1.13
ISOL22 0.94 0.41
DC9 2.98 0.30
DARC −0.50 −2.75
ALK6 8.26 1.49
BSR36 7.96 1.76
IDISP 10.73 1.86
S22 2.36 0.41
ADIM6 4.11 1.18
PCONF 1.63 −0.17
ACONF 0.76 0.25
SCONF 1.95 0.76
CYCONF 0.23 0.22

5
Table S3: Mean absolute deviations (MADs) for B3LYP-D3/def2-QZVP and B3LYP-gCP-D3/6-
31G∗ on the GMTKN30 benchmark set in kcal/mol. The reference values are the ’true’ coupled-
cluster or experimental data from the original publication.

GMTKN30 set B3LYP-D3/def2-QZVP B3LYP-gCP-D3/6-31G∗

MB08-165 5.68 14.16
W4-08 3.65 9.72
G21IP 3.55 4.57
PA 2.59 5.65
SIE11 8.69 9.67
BHPERI 1.93 1.45
BH76 5.39 6.47
BH76RC 2.23 8.23
RSE43 2.12 2.94
O3ADD6 2.99 4.72
G2RC 2.85 11.29
AL2X 1.61 4.12
NBPRC 1.89 3.54
ISO34 1.77 2.9
ISOL22 6.27 6.68
DC9 9.95 10.25
DARC 7.69 4.94
ALK6 3.28 4.77
BSR36 3.90 5.66
IDISP 4.36 6.22
S22 0.31 0.72
ADIM6 0.13 1.31
PCONF 0.58 0.41
ACONF 0.05 0.30
SCONF 0.38 1.14
CYCONF 0.28 0.50

6
3 molecular structure data for the fullerene mediated reac-

tions

All structures were optimized at the B3LYP-D3/def2-TZVP level of theory and are given in
atomic units. C60 fullerene

1.88738688375624 1.37126683784842 6.27123050399634 c

1.88738688375624 -1.37126683784842 6.27123050399634 c

3.69383994856467 -2.68373181427737 4.89122316064551 c

5.58122683232093 -1.31246497642896 3.44938788129725 c

5.58122683232093 1.31246497642896 3.44938788129725 c

3.69383994856467 2.68373181427737 4.89122316064551 c

-0.72091763967414 2.21875635128434 6.27123050399634 c

-2.33293848816420 0.00000000000000 6.27123050399634 c

-0.72091763967414 -2.21875635128434 6.27123050399634 c

-1.41092131134955 -4.34236929219021 4.89122316064551 c

2.97292230889054 -4.90248816556170 3.44938788129725 c

6.02677843672888 -2.68373181427737 1.11644939313305 c

6.45322415818651 -1.37126683784842 -1.11644939313305 c

6.45322415818651 1.37126683784842 -1.11644939313305 c

6.02677843672888 2.68373181427737 1.11644939313305 c

4.41475758823882 4.90248816556170 1.11644939313305 c

2.97292230889054 4.90248816556170 3.44938788129725 c

0.47646557240669 5.71363613003864 3.44938788129725 c

-1.41092131134955 4.34236929219021 4.89122316064551 c

-4.56583727443027 0.00000000000000 4.89122316064551 c

-5.28675491410441 2.21875635128434 3.44938788129725 c

-3.74385979951375 4.34236929219021 3.44938788129725 c

7
-3.29830819510578 5.71363613003864 1.11644939313305 c

-0.69000367167542 6.56112564347455 1.11644939313305 c

0.69000367167542 6.56112564347455 -1.11644939313305 c

3.29830819510578 5.71363613003864 -1.11644939313305 c

3.74385979951375 4.34236929219021 -3.44938788129725 c

5.28675491410441 2.21875635128434 -3.44938788129725 c

4.41475758823882 -4.90248816556170 1.11644939313305 c

0.72091763967414 -2.21875635128434 -6.27123050399634 c

1.41092131134955 -4.34236929219021 -4.89122316064551 c

-0.47646557240669 -5.71363613003863 -3.44938788129725 c

-2.97292230889054 -4.90248816556170 -3.44938788129725 c

-3.69383994856467 -2.68373181427737 -4.89122316064551 c

-1.88738688375624 1.37126683784842 -6.27123050399634 c

0.72091763967414 2.21875635128434 -6.27123050399634 c

2.33293848816420 0.00000000000000 -6.27123050399634 c

4.56583727443027 0.00000000000000 -4.89122316064551 c

5.28675491410441 -2.21875635128434 -3.44938788129725 c

3.74385979951375 -4.34236929219021 -3.44938788129725 c

0.69000367167542 -6.56112564347455 -1.11644939313305 c

-0.69000367167542 -6.56112564347455 1.11644939313305 c

-3.29830819510578 -5.71363613003864 1.11644939313305 c

-4.41475758823882 -4.90248816556170 -1.11644939313305 c

-6.02677843672888 -2.68373181427737 -1.11644939313305 c

-5.58122683232093 -1.31246497642896 -3.44938788129725 c

-5.58122683232093 1.31246497642896 -3.44938788129725 c

-3.69383994856467 2.68373181427737 -4.89122316064551 c

1.41092131134955 4.34236929219021 -4.89122316064551 c

-0.47646557240669 5.71363613003863 -3.44938788129725 c

8
-2.97292230889054 4.90248816556170 -3.44938788129725 c

-4.41475758823882 4.90248816556170 -1.11644939313305 c

-6.02677843672888 2.68373181427737 -1.11644939313305 c

-6.45322415818651 1.37126683784842 1.11644939313305 c

-6.45322415818651 -1.37126683784842 1.11644939313305 c

-5.28675491410441 -2.21875635128434 3.44938788129725 c

-3.74385979951375 -4.34236929219021 3.44938788129725 c

3.29830819510578 -5.71363613003864 -1.11644939313305 c

0.47646557240669 -5.71363613003864 3.44938788129725 c

-1.88738688375624 -1.37126683784842 -6.27123050399634 c

ethene

1.25184352280325 0.00000000000000 0.00000000000000 c

-1.25184352280325 0.00000000000000 0.00000000000000 c

-2.32884184987300 -1.74159823255505 0.00000000000000 h

-2.32884184987300 1.74159823255505 0.00000000000000 h

2.32884184987300 -1.74159823255505 0.00000000000000 h

2.32884184987300 1.74159823255505 0.00000000000000 h

benzene

2.27617465026315 1.31415004705205 0.00000000000000 c

2.27617465026315 -1.31415004705205 0.00000000000000 c

0.00000000000000 -2.62830009410407 0.00000000000000 c

-2.27617465026315 -1.31415004705205 0.00000000000000 c

-2.27617465026315 1.31415004705205 0.00000000000000 c

0.00000000000000 2.62830009410407 0.00000000000000 c

4.04816913141641 -2.33721153774839 0.00000000000000 h

0.00000000000000 -4.67442307549679 0.00000000000000 h

9
-4.04816913141641 -2.33721153774839 0.00000000000000 h

-4.04816913141641 2.33721153774839 0.00000000000000 h

0.00000000000000 4.67442307549679 0.00000000000000 h

4.04816913141641 2.33721153774839 0.00000000000000 h

naphthaline

4.57924618973961 1.33386364591621 0.00000000000000 c

2.34302115009961 2.63989828425373 0.00000000000000 c

0.00000000000000 1.34895924295542 0.00000000000000 c

0.00000000000000 -1.34895924295542 0.00000000000000 c

2.34302115009961 -2.63989828425373 0.00000000000000 c

4.57924618973961 -1.33386364591621 0.00000000000000 c

-2.33843820312462 4.68756109757994 0.00000000000000 h

6.35805590928715 2.34438641793785 0.00000000000000 h

2.33843820312462 4.68756109757994 0.00000000000000 h

-2.34302115009961 2.63989828425373 0.00000000000000 c

-2.34302115009961 -2.63989828425373 0.00000000000000 c

2.33843820312462 -4.68756109757994 0.00000000000000 h

6.35805590928715 -2.34438641793785 0.00000000000000 h

-4.57924618973961 -1.33386364591621 0.00000000000000 c

-4.57924618973961 1.33386364591621 0.00000000000000 c

-2.33843820312462 -4.68756109757994 0.00000000000000 h

-6.35805590928715 -2.34438641793785 0.00000000000000 h

-6.35805590928715 2.34438641793785 0.00000000000000 h

triphenylene

6.96526586917466 -1.31906509923542 0.00000000000000 c

4.70330540064175 -2.60575645455963 0.00000000000000 c

10
2.36529800111100 -1.33652697671625 0.00000000000000 c

2.36529800111100 1.33652697671625 0.00000000000000 c

4.70330540064175 2.60575645455963 0.00000000000000 c

6.96526586917466 1.31906509923542 0.00000000000000 c

-0.02518268587603 -2.71667164484079 0.00000000000000 c

-0.02518268587603 2.71667164484079 0.00000000000000 c

-2.34011531523499 1.38014466812455 0.00000000000000 c

-2.34011531523499 -1.38014466812455 0.00000000000000 c

-4.60830398604478 2.77030373143248 0.00000000000000 c

-6.39863553984014 1.79398957525480 0.00000000000000 h

-4.62497681977063 5.37256463720024 0.00000000000000 c

-2.34028904940401 6.69162973643567 0.00000000000000 c

-0.09500141459695 5.37606018599211 0.00000000000000 c

8.72951008268106 -2.35403727733576 0.00000000000000 h

4.75295831621519 -4.64438613943211 0.00000000000000 h

4.75295831621519 4.64438613943211 0.00000000000000 h

8.72951008268106 2.35403727733576 0.00000000000000 h

-6.40341112496885 6.38295885552632 0.00000000000000 h

-2.32609895771221 8.73699613286208 0.00000000000000 h

1.64567722362496 6.43837571468692 0.00000000000000 h

-4.60830398604478 -2.77030373143248 0.00000000000000 c

-0.09500141459695 -5.37606018599211 0.00000000000000 c

-4.62497681977063 -5.37256463720024 0.00000000000000 c

-2.34028904940401 -6.69162973643567 0.00000000000000 c

-6.39863553984014 -1.79398957525480 0.00000000000000 h

-6.40341112496885 -6.38295885552632 0.00000000000000 h

-2.32609895771221 -8.73699613286208 0.00000000000000 h

1.64567722362496 -6.43837571468692 0.00000000000000 h

11
corannulene

-5.98500933236723 -1.30593245628070 -0.16548374220139 c

-5.98500933236723 1.30593245628070 -0.16548374220139 c

-3.09148516758121 -5.28852680313861 -0.16548374220139 c

-3.78019128253173 -2.74646973075442 0.53406074800390 c

-1.84236416462092 -1.33855591767016 1.56719884731005 c

-3.78019128253173 2.74646973075442 0.53406074800390 c

-0.60745402280704 -6.09563744813172 -0.16548374220139 c

-3.09148516758121 5.28852680313861 -0.16548374220139 c

4.07436642308588 4.57442177103518 -0.16548374220139 c

5.60958209966962 2.46137866976137 -0.16548374220139 c

1.44390458595107 4.44388137343345 0.53406074800390 c

0.70372049123040 2.16582897063262 1.56719884731005 c

2.27728734678105 0.00000000000000 1.56719884731005 c

4.67257339316134 0.00000000000000 0.53406074800390 c

5.60958209966962 -2.46137866976137 -0.16548374220139 c

4.07436642308588 -4.57442177103518 -0.16548374220139 c

1.44390458595107 -4.44388137343345 0.53406074800390 c

0.70372049123040 -2.16582897063262 1.56719884731005 c

-0.60745402280704 6.09563744813172 -0.16548374220139 c

-1.84236416462092 1.33855591767016 1.56719884731005 c

4.83452277863069 -6.33468809215631 -0.88514605545583 h

7.51859608703224 -2.64037811725315 -0.88514605545583 h

7.51859608703224 2.64037811725315 -0.88514605545583 h

4.83452277863069 6.33468809215631 -0.88514605545583 h

-0.18777484916280 7.96653151177023 -0.88514605545583 h

-4.53069669045291 6.55543066633498 -0.88514605545583 h

12
 -7.63464732604724 2.28320912946791 -0.88514605545583 h

-7.63464732604724 -2.28320912946791 -0.88514605545583 h

-4.53069669045291 -6.55543066633498 -0.88514605545583 h

-0.18777484916280 -7.96653151177023 -0.88514605545583 h

4 single point energies for the applications section

Table S4: Absolute energies for all species involved in the fullerene mediated reactions in atomic
units. Results are shown for B3LYP/def2-QZVP, B3LYP/6-31G∗ , the DFT-D3 contribution for
B3LYP, and the gCP correction for 6-31G∗ in combination with a DFT method.

def2-QZVP 6-31G∗ DFT-D3 gCP

C60 −2285.66217 −2284.78783 −0.31589 0.10505
ethene −78.57276 −78.52760 −0.00394 0.01077
benzene −232.20013 −232.08934 −0.01895 0.02229
naphthaline −385.80918 −385.63393 −0.03659 0.03379
triphenylene −693.02787 −692.72326 −0.07498 0.05826
corannulene −767.97962 −767.65201 −0.08336 0.05518

Table S5: Absolute energies for all species involved in reaction 7 in atomic units. Results are
shown for B3LYP/def2-QZVP, B3LYP/6-31G∗ , the DFT-D3 contribution for B3LYP, and the
gCP correction for 6-31G∗ in combination with a DFT method.

def2-QZVP 6-31G∗ DFT-D3 gCP

2-methylfurane −269.30841 −269.17762 −0.01562 0.02555
cyclopropanone −744.18264 −743.83403 −0.05636 0.06337
TS syn-I −1013.47801 −1013.00294 −0.09227 0.09699
TS anti-I −1013.47610 −1013.00082 −0.09235 0.09724
TS syn-II −1013.47763 −1013.00190 −0.08842 0.09647
TS anti-II −1013.47548 −1013.00022 −0.08978 0.09713

13
Table S6: Absolute energies for all species involved in reaction 8 in atomic units. Results are
shown for B3LYP/def2-QZVP, B3LYP/6-31G∗ , the DFT-D3 contribution for B3LYP, and the
gCP correction for 6-31G∗ in combination with a DFT method.

def2-QZVP 6-31G∗ DFT-D3 gCP

anthracene −539.41107 −539.17441 −0.05417 0.04474
maleic anhydride −917.47848 −917.06588 −0.07972 0.06266
transition state −1456.82606 −1456.18884 −0.17473 0.11599
product −1456.89167 −1456.25940 −0.17366 0.11844

14