Supplementary material to: SCAN-based hybrid and double-hybrid density functionals from models without ﬁtted parameters

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Supplementary material to: SCAN-based hybrid and double-hybrid density functionals from models without fitted parameters

Kerwin Hui¹ and Jeng-Da Chai^{1, 2,}^⇤

1Department of Physics, National Taiwan University, Taipei 10617, Taiwan

2Center for Theoretical Sciences and Center for Quantum Science and Engineering, National Taiwan University, Taipei 10617, Taiwan

⇤ Author to whom correspondence should be addressed. Electronic mail: [email protected]

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LIST OF TABLES

I Nonhydrogen transfer barrier heights (in kcal/mol) of the NHTBH38/04 set [1]. . . 4

II Hydrogen transfer barrier heights (in kcal/mol) of the HTBH38/04 set [1, 2]. . . 7

III Interaction energies (in kcal/mol) of the S22 set [3, 4]. . . 12

IV Interaction energies (in kcal/mol) of the S66 set [5]. . . 14

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[1] Y. Zhao, N. Gonz´alez-Garc´ıa, and D. G. Truhlar, J. Phys. Chem. A 109, 2012 (2005); 110, 4942(E) (2006).

[2] Y. Zhao, B. J. Lynch, and D. G. Truhlar, J. Phys. Chem. A 108, 2715 (2004).

[3] P. Jureˇcka, J. ˇSponer, J. ˇCern´y, and P. Hobza, Phys. Chem. Chem. Phys. 8, 1985 (2006).

[4] T. Takatani, E. G. Hohenstein, M. Malagoli, M. S. Marshall, and C. D. Sherrill, J. Chem. Phys. 132, 144104 (2010).

[5] J. Rezac, K. E. Riley, and P. Hobza, J. Chem. Theory Comput. 7, 2427 (2011).

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TABLES

TABLE I: Nonhydrogen transfer barrier heights (in kcal/mol) of the NHTBH38/04 set [1].

Reaction Reference PBE SCAN PBE0 SCAN0 PBE0-DH SCAN0-DH PBE-QIDH SCAN-QIDH PBE0-2 SCAN0-2 Heavy-atom transfer reactions

H + N₂O ! OH + N₂

V^f 18.14 9.97 9.57 13.91 12.08 17.41 15.34 20.83 19.30 23.58 22.66

V^r 83.22 52.46 64.71 68.79 76.54 76.63 81.26 79.93 82.69 81.25 83.28

H + FH ! HF + H

V^f 42.18 27.07 28.83 33.74 33.42 38.71 37.24 41.88 40.16 43.35 41.87

V^r 42.18 27.07 28.83 33.74 33.42 38.71 37.24 41.88 40.16 43.35 41.87

H + ClH ! HCl + H

V^f 18.00 9.64 9.51 13.38 11.59 16.03 13.85 18.06 16.14 19.26 17.78

V^r 18.00 9.64 9.51 13.38 11.59 16.03 13.85 18.06 16.14 19.26 17.78

H + FCH₃ ! HF + CH3

V^f 30.38 18.51 20.38 25.71 25.25 30.23 28.79 32.79 31.06 33.87 32.35

V^r 57.02 40.99 46.44 49.75 53.03 54.86 56.60 57.43 58.24 58.38 58.85

H + F₂ ! HF + F

V^f 2.27 -9.86 -11.36 -4.60 -8.46 -0.44 -4.25 5.79 2.74 11.20 8.89

V^r 106.18 80.86 89.93 99.03 103.53 109.15 111.27 116.64 117.43 121.25 121.59

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Table I: NHTBH38/04 (continued).

Reaction Reference PBE SCAN PBE0 SCAN0 PBE0-DH SCAN0-DH PBE-QIDH SCAN-QIDH PBE0-2 SCAN0-2 CH₃+ FCl ! CH3F + Cl

V^f 7.43 -6.47 -4.62 0.79 1.39 4.97 5.08 7.86 7.84 10.02 10.03

V^r 60.17 41.63 45.99 53.46 55.24 60.14 60.54 64.14 63.88 66.55 66.21

Nucleophilic substitution reactions F^–+ CH₃F ! FCH₃+ F^–

V^f -0.34 -8.31 -8.37 -2.67 -3.20 -0.70 -1.16 -0.07 -0.40 -0.00 -0.17

V^r -0.34 -8.31 -8.37 -2.67 -3.20 -0.70 -1.16 -0.07 -0.40 -0.00 -0.17

F^–···CH3F ! FCH3···F^–

V^f 13.38 7.06 8.03 11.69 12.24 13.57 13.94 14.25 14.48 14.40 14.58

V^r 13.38 7.06 8.03 11.69 12.24 13.57 13.94 14.25 14.48 14.40 14.58

Cl^–+ CH₃Cl ! ClCH₃+ Cl^–

V^f 3.10 -3.80 -5.10 0.87 -0.53 2.92 1.92 3.89 3.27 4.32 3.91

V^r 3.10 -3.80 -5.10 0.87 -0.53 2.92 1.92 3.89 3.27 4.32 3.91

Cl^–···CH3Cl ! ClCH3···Cl^–

V^f 13.61 7.15 6.95 11.29 10.88 13.41 13.13 14.58 14.42 15.14 15.04

V^r 13.61 7.15 6.95 11.29 10.88 13.41 13.13 14.58 14.42 15.14 15.04

F^–+ CH₃Cl ! FCH₃+ Cl^–

V^f -12.54 -19.52 -21.98 -15.45 -17.67 -13.75 -15.21 -12.68 -13.56 -12.13 -12.64

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Reaction Reference PBE SCAN PBE0 SCAN0 PBE0-DH SCAN0-DH PBE-QIDH SCAN-QIDH PBE0-2 SCAN0-2

V^r 20.11 12.31 15.14 19.44 20.56 21.77 22.08 22.10 22.05 21.83 21.69

F^–···CH₃Cl ! FCH₃···Cl^–

V^f 2.89 -0.67 -1.65 1.66 0.94 2.95 2.56 3.82 3.63 4.29 4.20

V^r 29.62 21.45 25.09 28.35 30.19 30.86 31.73 31.47 31.80 31.38 31.51

OH^–+ CH₃F ! HOCH3+ F^–

V^f -2.78 -10.59 -10.24 -4.97 -5.24 -2.97 -3.27 -2.34 -2.56 -2.20 -2.34

V^r 17.33 9.14 9.15 15.94 15.34 18.22 17.64 18.70 18.23 18.50 18.22

OH^–···CH₃F ! HOCH₃···F^–

V^f 10.96 3.89 5.16 8.82 9.54 10.87 11.35 11.68 11.99 11.94 12.16

V^r 47.2 43.21 44.02 49.06 49.29 51.09 51.18 51.44 51.47 51.22 51.22

Unimolecular and association reactions H + N₂ ! HN2

V^f 14.69 5.19 4.35 8.50 6.40 11.54 9.42 14.77 13.19 17.32 16.25

V^r 10.72 9.08 9.70 11.64 11.75 12.55 12.48 12.41 12.32 11.91 11.71

H + CO ! HCO

V^f 3.17 -1.69 -3.48 0.31 -2.18 1.83 -0.41 3.08 1.37 3.85 2.59

V^r 22.68 24.66 24.12 25.47 24.68 25.51 24.71 25.03 24.42 24.52 24.10

H + C₂H₄ ! CH3CH₂

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V^f 1.72 -0.14 -4.01 0.67 -3.68 1.50 -1.73 2.89 0.76 4.24 2.80

V^r 41.75 40.20 43.00 44.12 45.16 45.72 46.03 46.14 46.31 46.18 46.38

CH₃+ C₂H₄ ! CH3CH₂CH₂

V^f 6.85 1.50 0.93 4.02 2.47 5.24 4.28 6.64 6.15 7.93 7.67

V^r 32.97 29.76 30.62 34.47 33.72 36.89 35.78 38.33 37.45 39.12 38.50

HCN ! HCN

V^f 48.16 45.60 46.27 46.37 46.47 47.30 47.11 48.45 48.18 49.35 49.09

V^r 33.11 30.50 32.14 32.51 33.42 33.31 33.69 33.71 33.79 33.92 33.90

MSE -8.52 -7.48 -3.13 -3.28 -0.32 -0.83 1.39 0.87 2.34 1.94

MAE 8.62 7.62 3.63 3.84 1.57 2.24 1.62 1.63 2.44 2.03

rms 10.61 8.72 4.63 4.63 2.19 2.82 2.58 2.55 3.71 3.43

Max( ) -30.76 -18.51 -14.43 -10.73 -6.59 -6.52 -3.29 -2.02 -1.97 -0.58

Max(+) 1.98 1.44 2.79 3.41 3.97 5.09 10.46 11.25 15.07 15.41

TABLE II: Hydrogen transfer barrier heights (in kcal/mol) of the HTBH38/04 set [1, 2].

Reaction Reference PBE SCAN PBE0 SCAN0 PBE0-DH SCAN0-DH PBE-QIDH SCAN-QIDH PBE0-2 SCAN0-2 H + HCl ! H₂+ Cl

V^f 5.70 0.56 -1.05 2.94 0.31 4.88 2.18 6.56 4.26 7.64 5.83

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Table II: HTBH38/04 (continued).

V^r 8.70 -1.95 0.09 1.66 2.39 3.90 4.23 5.26 5.20 5.90 5.79

OH + H₂ ! H + H2O

V^f 5.10 -6.36 -2.01 -0.02 1.98 3.16 4.11 4.79 4.95 5.51 5.45

V^r 21.20 13.69 11.36 17.31 14.02 20.24 17.06 23.24 20.58 25.39 23.30

CH₃+ H₂ ! H + CH4

V^f 12.10 3.82 7.47 6.89 8.99 8.83 10.21 10.13 10.81 10.84 11.26

V^r 15.30 9.32 7.36 11.90 9.18 13.92 11.47 15.64 13.55 16.72 15.05

OH + CH₄ ! CH3+ H₂O

V^f 6.70 -5.65 -1.58 1.62 3.48 4.91 5.87 6.17 6.44 6.50 6.53

V^r 19.60 8.91 11.90 13.94 15.33 16.90 17.56 19.10 19.34 20.50 20.59

H + H₂ ! H2+ H

V^f 9.60 3.64 2.53 5.63 3.58 7.46 5.59 9.15 7.56 10.24 9.03

V^r 9.60 3.64 2.53 5.63 3.58 7.46 5.59 9.15 7.56 10.24 9.03

OH + NH₃ ! H2O + NH₂

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V^f 3.20 -11.94 -7.40 -2.28 -0.07 2.16 3.31 3.97 4.43 4.60 4.78

V^r 12.70 -0.71 3.31 7.41 9.37 11.49 12.47 13.73 14.13 14.91 15.07

HCl + CH₃ ! Cl + CH₄

V^f 1.70 -5.94 -3.08 -2.49 -0.90 -0.67 0.21 0.30 0.67 0.74 0.91

V^r 7.90 -2.95 -2.04 1.25 1.38 3.45 3.51 4.51 4.34 4.88 4.66

OH + C₂H₆ ! H₂O + C₂H₅

V^f 3.40 -9.03 -4.49 -1.23 0.77 2.22 3.37 3.58 3.96 4.00 4.08

V^r 19.90 10.75 13.13 15.65 16.62 18.30 18.71 20.25 20.34 21.52 21.51

F + H₂ ! HF + H

V^f 1.80 -12.97 -7.77 -4.90 -2.56 -0.73 0.29 1.48 1.67 2.44 2.44

V^r 33.40 25.12 22.61 28.40 24.89 31.46 28.03 35.11 32.33 37.88 35.75

O + CH₄ ! OH + CH₃

V^f 13.70 -0.79 1.76 7.16 7.98 11.53 11.82 13.66 13.56 14.42 14.23

V^r 8.10 -0.57 3.31 3.94 6.33 6.48 7.86 8.07 8.83 8.93 9.43

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Reaction Reference PBE SCAN PBE0 SCAN0 PBE0-DH SCAN0-DH PBE-QIDH SCAN-QIDH PBE0-2 SCAN0-2 H + PH₃ ! PH2+ H₂

V^f 3.10 -1.78 -2.65 0.35 -1.67 1.86 -0.08 3.02 1.28 3.70 2.29

V^r 23.20 17.91 19.24 20.12 20.47 21.43 21.69 22.31 22.36 22.79 22.82

H + HO ! H2+ O

V^f 10.70 3.74 3.39 7.13 5.69 9.66 7.81 11.87 10.16 13.34 11.94

V^r 13.10 -1.98 1.94 5.33 7.14 9.62 10.52 11.95 12.15 12.94 12.95

H + H₂S ! H2+ HS

V^f 3.50 -1.22 -2.43 1.05 -1.10 2.69 0.56 3.95 2.10 4.69 3.21

V^r 17.30 9.10 11.25 12.06 13.02 13.75 14.34 14.70 14.88 15.12 15.20

O + HCl ! OH + Cl

V^f 9.80 -10.54 -3.88 2.22 4.86 8.05 9.21 11.10 11.44 12.38 12.46

V^r 10.40 -7.33 -1.30 2.74 5.48 7.12 8.55 9.71 10.39 11.04 11.42

NH₂+ CH₃ ! CH4+ NH

V^f 8.00 0.71 4.52 5.05 7.38 7.26 8.59 8.44 9.15 9.00 9.44

V^r 22.40 10.56 12.29 16.42 16.77 19.62 19.63 21.32 21.03 22.03 21.69

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NH₂+ C₂H₅ ! C₂H₆+ NH

V^f 7.50 2.89 5.99 6.88 8.82 8.71 9.85 9.53 10.16 9.86 10.27

V^r 18.30 7.50 9.61 13.69 14.21 16.98 17.24 18.67 18.55 19.38 19.15

C₂H₆+ NH₂ ! NH₃+ C₂H₅

V^f 10.40 1.43 5.26 7.25 9.01 9.81 10.88 10.69 11.07 10.87 10.97

V^r 17.40 9.98 12.17 14.45 15.41 16.57 17.06 17.60 17.76 18.08 18.12

NH₂+ CH₄ ! CH₃+ NH₃

V^f 14.50 4.39 7.85 9.87 11.51 12.37 13.25 13.29 13.55 13.49 13.53

V^r 17.80 7.71 10.62 12.50 13.92 15.03 15.78 16.47 16.75 17.18 17.30

s-trans cis-C₅H₈ ! s-trans cis-C₅H₈

V^f 38.40 31.20 33.63 35.58 37.16 37.35 38.19 37.23 37.54 36.46 36.57

V^r 38.40 31.20 33.63 35.58 37.16 37.35 38.19 37.23 37.54 36.46 36.57

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MSE -9.67 -7.49 -4.60 -3.99 -1.87 -1.81 -0.28 -0.56 0.50 0.19

MSE 9.67 7.49 4.60 4.06 1.93 2.00 0.99 1.14 1.39 1.18

rms 10.37 7.94 4.88 4.46 2.19 2.48 1.30 1.43 1.74 1.45

Max( ) -20.34 -13.68 -7.77 -8.51 -4.80 -5.37 -3.44 -3.56 -3.02 -3.24

Max(+) -4.61 -1.51 -0.62 1.32 1.21 2.35 2.04 2.66 4.48 2.77

TABLE III: Interaction energies (in kcal/mol) of the S22 set [3, 4].

Complex Reference PBE SCAN PBE0 SCAN0 PBE0-DH SCAN0-DH PBE-QIDH SCAN-QIDH PBE0-2 SCAN0-2

Hydrogen bonded complexes

NH₃ dimer (C2h) -3.17 -2.83 -3.14 -2.77 -3.11 -2.83 -3.15 -2.90 -3.15 -2.93 -3.12

H₂O dimer (Cs) -5.02 -4.91 -5.39 -4.92 -5.38 -4.96 -5.34 -4.94 -5.22 -4.89 -5.09

Formic acid dimer (C2h) -18.80 -18.08 -20.63 -18.86 -20.75 -19.21 -20.49 -19.08 -19.87 -18.75 -19.28 Formamide dimer (C2h) -16.12 -14.69 -16.38 -15.27 -16.59 -15.64 -16.60 -15.69 -16.34 -15.55 -16.01 Uracil dimer (C2h) -20.69 -18.45 -20.32 -19.16 -20.65 -19.72 -20.81 -19.95 -20.68 -19.91 -20.43 2-pyridone ... 2-aminopyridine (C1) -17.00 -15.27 -16.69 -15.35 -16.53 -15.84 -16.73 -16.26 -16.88 -16.42 -16.86 Adenine ... thymine WC (C1) -16.74 -14.29 -15.88 -14.50 -15.83 -15.09 -16.10 -15.54 -16.25 -15.69 -16.17

Dispersion complexes

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Table III: S22 interaction energies (continued).

CH₄ dimer (D3d) -0.53 -0.08 -0.37 -0.04 -0.31 -0.09 -0.32 -0.18 -0.36 -0.25 -0.38

C₂H₄ dimer (D2d) -1.50 -0.31 -1.07 -0.35 -1.04 -0.58 -1.15 -0.84 -1.26 -1.00 -1.31

Benzene ... CH₄ -1.45 -0.01 -0.89 -0.08 -0.82 -0.41 -0.97 -0.79 -1.19 -1.04 -1.33

Benzene dimer (C2h) -2.62 1.90 -1.13 1.80 -0.57 0.60 -1.03 -0.91 -1.95 -1.94 -2.66

Pyrazine dimer (Cs) -4.20 0.73 -2.71 0.53 -2.14 -0.82 -2.64 -2.45 -3.61 -3.57 -4.35

Uracil dimer (C2) -9.74 -2.69 -8.00 -3.30 -7.32 -4.99 -7.76 -6.81 -8.57 -7.91 -9.14

Indole Benzene (C1) -4.59 2.24 -2.19 2.02 -1.39 0.17 -2.17 -2.12 -3.59 -3.67 -4.68

Adenine ... thymine (C1) -11.66 -1.32 -8.69 -2.14 -7.73 -4.86 -8.65 -7.83 -10.21 -9.69 -11.32

Mixed complexes

Ethene ... Ethine (C2v) -1.51 -1.16 -1.35 -1.18 -1.38 -1.26 -1.46 -1.36 -1.51 -1.41 -1.53

Benzene ... H₂O (Cs) -3.29 -2.04 -3.30 -2.21 -3.19 -2.54 -3.23 -2.83 -3.28 -2.98 -3.30

Benzene ... NH₃ (Cs) -2.32 -0.92 -2.00 -1.03 -1.89 -1.36 -1.99 -1.72 -2.14 -1.94 -2.24

Benzene ... HCN (Cs) -4.55 -2.81 -4.08 -3.28 -4.29 -3.83 -4.55 -4.25 -4.73 -4.46 -4.79

Benzene dimer (C2v) -2.71 -0.10 -1.50 -0.28 -1.43 -0.95 -1.79 -1.70 -2.28 -2.19 -2.60

Indole ... Benzene (Cs) -5.62 -2.03 -4.07 -2.36 -3.97 -3.32 -4.48 -4.37 -5.14 -5.03 -5.57

Phenol dimer (C1) -7.09 -3.87 -5.92 -4.18 -5.83 -4.96 -6.18 -5.76 -6.58 -6.23 -6.82

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Table III: S22 interaction energies (continued).

MSE 2.72 0.69 2.45 0.85 1.75 0.60 1.03 0.28 0.61 0.09

MAE 2.72 0.92 2.46 1.11 1.78 0.84 1.05 0.43 0.61 0.19

rms 3.73 1.22 3.45 1.54 2.49 1.19 1.42 0.59 0.78 0.25

Max( ) 0.11 -1.83 -0.06 -1.95 -0.41 -1.69 -0.28 -1.07 0.05 -0.48

Max(+) 10.34 2.97 9.52 3.93 6.80 3.01 3.83 1.45 1.97 0.60

TABLE IV: Interaction energies (in kcal/mol) of the S66 set [5].

Complex Reference PBE SCAN PBE0 SCAN0 PBE0-DH SCAN0-DH PBE-QIDH SCAN-QIDH PBE0-2 SCAN0-2 Hydrogen bonded complexes

Water ... Water -4.918 -4.87 -5.32 -4.90 -5.33 -4.94 -5.30 -4.93 -5.20 -4.88 -5.08

Water ... MeOH -5.592 -5.16 -5.95 -5.20 -5.88 -5.33 -5.86 -5.42 -5.79 -5.43 -5.70

Water ... MeNH2 -6.908 -7.15 -7.46 -7.01 -7.36 -7.01 -7.33 -6.99 -7.24 -6.94 -7.13

Water ... Peptide -8.103 -7.28 -8.68 -7.49 -8.63 -7.72 -8.56 -7.83 -8.39 -7.82 -8.21

MeOH ... MeOH -5.757 -5.08 -5.89 -5.10 -5.80 -5.26 -5.82 -5.40 -5.80 -5.46 -5.75

MeOH ... MeNH2 -7.554 -7.19 -7.83 -7.05 -7.67 -7.16 -7.69 -7.28 -7.68 -7.32 -7.62

MeOH ... Peptide -8.230 -7.18 -8.53 -7.30 -8.43 -7.56 -8.42 -7.74 -8.33 -7.78 -8.20

MeOH ... Water -5.009 -4.78 -5.27 -4.79 -5.26 -4.85 -5.26 -4.88 -5.18 -4.87 -5.09

MeNH2 ... MeOH -3.059 -2.22 -2.76 -2.17 -2.68 -2.31 -2.76 -2.50 -2.84 -2.61 -2.86

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Table IV: S66 interaction energies (continued).

MeNH2 ... MeNH2 -4.160 -3.08 -3.87 -3.01 -3.75 -3.24 -3.86 -3.51 -3.97 -3.67 -4.01

MeNH2 ... Peptide -5.419 -3.39 -4.96 -3.53 -4.84 -3.98 -4.98 -4.43 -5.12 -4.67 -5.17

MeNH2 ... Water -7.266 -7.14 -7.87 -7.06 -7.72 -7.15 -7.68 -7.22 -7.59 -7.22 -7.49

Peptide ... MeOH -6.187 -4.53 -5.69 -4.72 -5.69 -5.09 -5.85 -5.44 -5.98 -5.63 -6.02

Peptide ... MeNH2 -7.454 -6.12 -7.06 -6.12 -6.96 -6.44 -7.12 -6.78 -7.27 -6.96 -7.32

Peptide ... Peptide -8.630 -6.36 -8.00 -6.64 -7.98 -7.16 -8.16 -7.62 -8.31 -7.84 -8.34

Peptide ... Water -5.124 -4.32 -4.88 -4.46 -4.98 -4.64 -5.08 -4.78 -5.11 -4.83 -5.08

Uracil ... Uracil (BP) -17.182 -15.49 -17.25 -15.98 -17.41 -16.47 -17.53 -16.70 -17.42 -16.69 -17.20

Water ... Pyridine -6.857 -6.82 -7.13 -6.64 -7.01 -6.69 -7.02 -6.75 -7.01 -6.76 -6.96

MeOH ... Pyridine -7.410 -6.92 -7.42 -6.73 -7.24 -6.86 -7.31 -7.04 -7.38 -7.14 -7.39

AcOH ... AcOH -19.093 -18.59 -21.09 -19.24 -21.12 -19.58 -20.87 -19.49 -20.29 -19.20 -19.73 AcNH2 ... AcNH2 -16.265 -15.02 -16.64 -15.48 -16.78 -15.85 -16.81 -15.94 -16.59 -15.85 -16.30 AcOH ... Uracil -19.491 -18.31 -20.45 -18.96 -20.62 -19.39 -20.56 -19.45 -20.21 -19.28 -19.81 AcNH2 ... Uracil -19.189 -17.67 -19.53 -18.31 -19.78 -18.79 -19.85 -18.93 -19.64 -18.83 -19.33

Dispersion complexes

Benzene ... Benzene (pi-pi) -2.822 1.22 -1.34 1.18 -0.83 0.18 -1.24 -1.13 -2.05 -2.04 -2.68 Pyridine ... Pyridine (pi-pi) -3.895 0.48 -2.39 0.34 -1.90 -0.79 -2.34 -2.20 -3.20 -3.17 -3.86 Uracil ... Uracil (pi-pi) -9.829 -2.51 -8.00 -3.15 -7.30 -4.91 -7.75 -6.77 -8.58 -7.90 -9.15

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Complex Reference PBE SCAN PBE0 SCAN0 PBE0-DH SCAN0-DH PBE-QIDH SCAN-QIDH PBE0-2 SCAN0-2 Benzene ... Pyridine (pi-pi) -3.439 0.81 -1.94 0.71 -1.44 -0.37 -1.87 -1.74 -2.71 -2.68 -3.35 Benzene ... Uracil (pi-pi) -5.713 0.36 -3.81 0.01 -3.18 -1.49 -3.69 -3.22 -4.62 -4.34 -5.30 Pyridine ... Uracil (pi-pi) -6.819 -0.74 -4.97 -1.12 -4.37 -2.62 -4.86 -4.34 -5.76 -5.44 -6.42

Benzene ... Ethene -1.432 0.76 -0.81 0.82 -0.45 0.32 -0.60 -0.36 -0.97 -0.84 -1.27

Uracil ... Ethene -3.380 -0.34 -2.56 -0.52 -2.27 -1.22 -2.47 -2.01 -2.83 -2.51 -3.08

Uracil ... Ethyne -3.738 -1.03 -3.16 -1.24 -2.92 -1.88 -3.06 -2.57 -3.34 -3.00 -3.54

Pyridine ... Ethene -1.872 0.45 -1.24 0.48 -0.88 -0.06 -1.04 -0.77 -1.43 -1.27 -1.73

Pentane ... Pentane -3.776 0.42 -1.90 0.38 -1.61 -0.45 -2.02 -1.46 -2.59 -2.12 -2.95

Neopentane ... Pentane -2.613 0.18 -0.98 0.23 -0.82 -0.26 -1.14 -0.89 -1.55 -1.31 -1.80 Neopentane ... Neopentane -1.777 0.14 -1.16 0.18 -0.99 -0.35 -1.31 -1.01 -1.72 -1.45 -1.98 Cyclopentane ... Neopentane -2.404 0.11 -1.25 0.18 -1.07 -0.41 -1.45 -1.18 -1.96 -1.69 -2.27 Cyclopentane ... Cyclopentane -2.997 0.05 -0.59 0.16 -0.48 -0.16 -0.73 -0.59 -1.04 -0.89 -1.24 Benzene ... Cyclopentane -3.575 0.30 -1.96 0.18 -1.66 -0.72 -2.07 -1.80 -2.72 -2.52 -3.17 Benzene ... Neopentane -2.895 0.09 -1.57 0.00 -1.36 -0.67 -1.70 -1.49 -2.20 -2.04 -2.54

Uracil ... Pentane -4.848 0.52 -2.89 0.27 -2.43 -0.91 -2.88 -2.25 -3.58 -3.09 -4.04

Uracil ... Cyclopentane -4.138 0.58 -2.25 0.44 -1.83 -0.58 -2.24 -1.77 -2.90 -2.54 -3.35 Uracil ... Neopentane -3.712 0.08 -2.26 -0.07 -1.93 -0.87 -2.24 -1.80 -2.73 -2.39 -3.06

Ethene ... Pentane -2.005 0.01 -1.12 0.03 -0.98 -0.36 -1.18 -0.85 -1.45 -1.17 -1.62

Ethyne ... Pentane -1.748 -0.09 -1.14 -0.06 -0.96 -0.39 -1.10 -0.82 -1.33 -1.12 -1.49

(17)

Peptide ... Pentane -4.264 0.07 -2.69 -0.07 -2.34 -0.97 -2.68 -2.00 -3.19 -2.65 -3.51

Mixed complexes

Benzene ... Benzene (TS) -2.876 -0.19 -1.66 -0.36 -1.56 -1.03 -1.92 -1.79 -2.40 -2.29 -2.72 Pyridine ... Pyridine (TS) -3.535 -0.75 -2.31 -0.97 -2.26 -1.68 -2.64 -2.46 -3.11 -2.95 -3.42 Benzene ... Pyridine (TS) -3.331 -0.61 -2.13 -0.84 -2.08 -1.53 -2.45 -2.30 -2.91 -2.78 -3.22 Benzene ... Ethyne (CH-pi) -2.867 -1.23 -2.31 -1.48 -2.36 -1.94 -2.59 -2.38 -2.82 -2.64 -2.95 Ethyne ... Ethyne (TS) -1.524 -1.20 -1.38 -1.21 -1.41 -1.28 -1.47 -1.35 -1.51 -1.39 -1.51 Benzene ... AcOH (OH-pi) -4.707 -2.32 -4.31 -2.65 -4.16 -3.28 -4.31 -3.86 -4.52 -4.18 -4.63 Benzene ... AcNH2 (NH-pi) -4.361 -2.34 -3.82 -2.59 -3.78 -3.10 -3.98 -3.59 -4.18 -3.86 -4.28 Benzene ... Water (OH-pi) -3.277 -1.98 -3.33 -2.17 -3.21 -2.52 -3.25 -2.82 -3.30 -2.98 -3.31 Benzene ... MeOH (OH-pi) -4.188 -1.86 -3.75 -2.03 -3.52 -2.61 -3.66 -3.21 -3.91 -3.58 -4.06 Benzene ... MeNH2 (NH-pi) -3.231 -0.77 -2.52 -0.90 -2.30 -1.48 -2.50 -2.13 -2.81 -2.55 -3.03 Benzene ... Peptide (NH-pi) -5.282 -1.68 -4.05 -2.01 -3.87 -2.90 -4.23 -3.86 -4.73 -4.45 -5.06 Pyridine ... Pyridine (CH-N) -4.146 -2.49 -3.01 -2.60 -3.15 -3.02 -3.51 -3.43 -3.81 -3.66 -3.95 Ethyne ... Water (CH-O) -2.850 -2.63 -2.82 -2.74 -2.96 -2.81 -3.03 -2.83 -3.01 -2.81 -2.95 Ethyne ... AcOH (OH-pi) -4.868 -4.10 -5.23 -4.30 -5.21 -4.50 -5.18 -4.61 -5.07 -4.62 -4.94

Pentane ... AcOH -2.912 0.07 -1.82 0.02 -1.54 -0.57 -1.76 -1.26 -2.10 -1.71 -2.31

Pentane ... AcNH2 -3.534 -0.26 -2.35 -0.32 -2.05 -0.98 -2.31 -1.75 -2.68 -2.23 -2.91

(18)

Benzene ... AcOH -3.801 -0.53 -2.83 -0.81 -2.61 -1.60 -2.88 -2.46 -3.29 -2.99 -3.57

Peptide ... Ethene -2.999 -0.95 -2.34 -1.06 -2.22 -1.49 -2.38 -1.96 -2.58 -2.25 -2.70

Pyridine ... Ethyne -3.991 -3.64 -3.73 -3.65 -3.82 -3.78 -3.97 -3.89 -4.06 -3.94 -4.07

MeNH2 ... Pyridine -3.968 -1.73 -3.30 -1.73 -3.05 -2.25 -3.24 -2.88 -3.56 -3.28 -3.77

MSE 2.22 0.61 2.09 0.77 1.56 0.58 1.00 0.33 0.66 0.19

MAE 2.23 0.85 2.10 1.01 1.58 0.81 1.01 0.49 0.67 0.27

rms 2.75 1.04 2.61 1.25 1.98 1.01 1.27 0.63 0.83 0.40

Max( ) -0.24 -2.00 -0.15 -2.03 -0.49 -1.77 -0.40 -1.20 -0.10 -0.64

Max(+) 7.32 2.41 6.68 2.53 4.92 2.27 3.06 1.95 2.11 1.76