Supplementary Information for

(1)

Supplementary Information for

Excited States and Excitonic Interactions in Prototypic Polycyclic Aromatic Hydrocarbon

Dimers as Models for Graphitic Interaction in Carbon Dots

Baimei Shi,

a

_{Dana Nachtigallová,*}

,b,c

_{Adélia J. A. Aquino,}

a

_{Francisco B. C. Machado,}

d

_{and Hans}

Lischka

a,

_*

a

_{School of Pharmaceutical Sciences and Technology, Tianjin University, Tianjin 300072, P.R.}

China

b

_{Institute of Organic Chemistry and Biochemistry v.v.i., The Czech Academy of Sciences,}

Flemingovo nám. 2, 16610 Prague 6, Czech Republic

c

_{Regional Centre of Advanced Technologies and Materials, Palacký University, 78371 Olomouc,}

Czech Republic

d

_{Departamento de Química, Instituto Tecnológico de Aeronáutica, São José dos Campos}

12228-900, São Paulo, Brazil

(2)

Page no.

Figure S1. Natural Transition Orbitals of pyrene monomer (the first row) and dimer

(the second and third row) calculated for the S1 state at SOS-ADC(2)/def2-TZVP

levelFigure S1. Natural Transition Orbitals of pyrene monomer (the first row) and

dimer (the second and third row) calculated for the S1 state at

SOS-ADC(2)/def2-TZVP level using Ci symmetry labeling

p. S4

Table S1. Excitation energies, oscillator strengths, CT values and PRNTO for the

lowest few dark and bright excited states of the pyrene dimer calculated using

several computational methods and using Ci symmetry labeling

p. S4-5

Table S2. Excited states properties of the lowest four states (dominant contributions

and percentage using NTOs, charge transfer CT and participation ratios PR

NTO

) of

pyrene dimer calculated at several computational levels and using Ci symmetry

labeling

p. S5-6

Figure S2. Natural Transition Orbitals of circum-1-pyrene monomer (the first row)

and dimer (the second and third row) calculated for the S1 state at

SOS-ADC(2)/SV(P) level using Ci symmetry labeling

p. S7

Table S3. Excitation energies, oscillator strengths, CT values and PRNTO for the

lowest few dark and bright excited states of the circum-1-pyrene dimer calculated

using several computational methods and using Ci symmetry labeling

p. S7

Table S4. Excited states properties of the lowest four states (dominant contributions

and percentage using NTOs, charge transfer CT and participation ratios PRNTO) of

circum-1-pyrene dimer calculated at several computational levelsTable S4. Excited

states properties of the lowest four states (dominant contributions and percentage

using NTOs, charge transfer CT and participation ratios PRNTO) of

circum-1-pyrene dimer calculated at several computational levels and using Ci symmetry

labeling

p. S8

Figure S3. Natural Transition Orbitals of coronene monomer (the first row) and

dimer (the second and third row) calculated for the S1 state at

SOS-ADC(2)/def2-TZVP level using Ci symmetry labeling

p. S9

Table S5.

Excitation energies, oscillator strengths and CT values for the lowest

bright and dark excited states of the coronene dimer calculated using several

computational methods and using Ci symmetry labeling

p. S9-10

Table S6 Excited states properties of the lowest four states and selected higher states

(dominant contributions and percentage using NTOs, charge transfer CT and

participation ratios PRNTO) of coronene dimer calculated at several computational

levels and using Ci symmetry labeling

p. S10-13

Figure S4.

Natural Transition Orbitals of circum-1-coronene monomer (the first

row) and dimer (the second and third row) calculated for the S1 state at

SOS-ADC(2)/SV(P) level using Ci symmetry labeling

p. S13

Table S7 Excited states properties of the lowest four states (dominant contributions

and percentage using NTOs, charge transfer CT and participation ratios PRNTO) of

circum-1-coronene dimer calculated at several computational levels and Ci

(3)

Table S8.

Excitation energies, oscillator strengths and CT values for the lowest

bright and dark excited states of the circum-1-coronene dimer calculated using

several computational levels and Ci symmetry labeling

p. S14

Figure S5. Definition of x and y for pyrene and coronene dimer structures of a)

pyrene and b) coronene

p. S15

Table S9. Adiabatic energy (in eV) comparison for different S1 optimized pyrene

dimer calculated at SOS-ADC(2)/SV(P) levela

p. S15

Table S10. Adiabatic energy (in eV) comparison for different S1 optimized

coronene dimer calculated at SOS-ADC(2)/SV(P) levela

p. S15

Cartesian coordinates of the fully optimized geometries p. S16-40

(4)

Figure S1. Natural Transition Orbitals of pyrene monomer (the first row) and dimer (the second

and third row) calculated for the S

1

state at SOS-ADC(2)/def2-TZVP level using Ci symmetry

labeling

Table S1.

Excitation energies, oscillator strengths, CT values and PR

NTO

for the lowest few dark

and bright excited states of the pyrene dimer calculated using several computational methods and

using Ci symmetry labeling

State

(5)

-6

4

1

_Ag

_4.28

_0.00

-12

6

1

_Au

_5.02

_0.31

13

9

1

_Au

_5.16

_0.12

16

10

1

_Au

_5.37

_0.56

SOS-ADC(2)

b

1

_Au

_3.66

_0.00

_0.03

_3.80

2

1

_Ag

_3.66

_0.00

_0.04

_3.74

3

1

_Ag

_4.05

_0.00

_0.03

_2.15

4

2

1

_Au

_4.08

_0.46

_0.19

_1.57

5

4

1

_Ag

_4.59

_0.00

_0.99

_1.99

6

3

1

_Au

_4.64

_0.00

_0.08

_2.26

11

5

1

_Au

_4.97

_0.09

_0.31

_3.59

12

6

1

_Au

_5.08

_0.33

_0.22

_3.22

18

9

1

_Au

_5.34

_0.16

_0.74

_2.36

24

12

1

_Au

_5.75

_1.90

_0.16

_2.04

30

15

1

_Au

_6.02

_0.33

_0.77

_1.88

TD-CAM-B3LYP

b

1

2

1

_Ag

_3.94

_0.00

_0.26

_2.30

2

1

_Au

_3.96

_0.38

_0.33

_1.32

3

1

_Ag

_4.00

_0.00

_0.26

_3.77

4

2

1

_Au

_4.00

_0.00

_0.26

_3.84

5

4

1

_Ag

_4.26

_0.00

_0.51

_2.00

6

3

1

_Au

_4.41

_0.08

_0.43

_1.29

10

5

1

_Au

_4.99

_0.17

_0.39

_2.47

15

8

1

_Au

_5.25

_0.34

_2.10

24

12

1

_Au

_5.76

_1.23

_0.26

_2.20

26

13

1

_Au

_5.95

_0.23

_-

-55

28

1

_Au

_6.88

_0.46

_-

-57

29

1

_Au

_6.99

_1.03

_-

-86

43

1

_Au

_7.65

_0.98

_-

-88

44

1

_Au

_7.65

_0.32

_-

-a

_{SV(P) basis set;}

b

_{def2-TZVP basis set;}

c

_{relative to DFT/MRCI results.}

Table S2. Excited states properties of the lowest four states (dominant contributions and

percentage using NTOs, charge transfer CT and participation ratios PR

NTO

) of pyrene dimer

calculated at several computational levels and using Ci symmetry labeling

State. no

State Dominant contributions %

CT

PR

NTO

(6)

2

1

_Ag

H-2/L

H/L+3

H-1/L+2

H-3/L+1

28

24

18

14 -

-

3

2

1

_Au

_H/L

₇₉

_-

4

3

1

_Ag

H/L+1

H-1/L

50

33 -

-

SC-NEVPT2

a

1

2

1

_Ag

H/L+3

H-2/L

H-1/L+2

H-3/L+1

25

19

15

2

1

_Au

H/L+3

H-3/L

H-2/L+1

H-1/L+2

26

21

16

3

2

1

_Au

_H/L

₆₆

4

3

1

_Au

_H-1/L+1

₆₃

5

3

1

_Ag

H/L+1

H-1/L

51

26 SOS-ADC(2)

b

1

_Au

H/L+2

H-3/L

H-2/ L+1

H-1/L+3

33

22

21

19

0.03

3.80

2

1

_Ag

H-2/L

H/L+3

H-1/L+2

H-3/L+1

32

28

20

16

0.04

3.74

3

1

_Ag

H/L+1

H-1/L

51

41

0.03

2.15

4

2

1

_Au

_H/L

_{77 0.19}

_1.57

TD-CAM-B3LYP

b

1

2

1

_Ag

H-1/L

H/L+1

50

43

0.26

2.30

2

1

_Au

_H/L

_{88 0.33}

_1.32

3

1

_Ag

H-2/L

H/L+3

H-1/L+2

H-3/L+1

35

28

21

14

0.26

3.77

4

2

1

_Au

H/L+2

H-3/L

H-2/L+1

H-1/L+3

37

21

19

0.26

3.84

(7)

Figure S2.

Natural Transition Orbitals of circum-1-pyrene monomer (the first row) and dimer (the

second and third row) calculated for the S

1

state at SOS-ADC(2)/SV(P) level using C

i

symmetry

labeling

Table S3. Excitation energies, oscillator strengths, CT values and PR

NTO

for the lowest few dark

and bright excited states of the circum-1-pyrene dimer calculated using several computational

methods and using Ci symmetry labeling

State no.

State

∆E(eV)

f

CT

PR

NTO

SOS-ADC(2)

a

1

2

1

_Ag

_2.50

_0.00

_0.29

_2.76

2

1

_Au

_2.54

_0.55

_0.37

_1.06

3

2

1

_Au

_2.57

_0.00

_0.26

_3.88

4

3

1

_Ag

_2.66

_0.00

_0.26

_1.98

5

4

1

_Ag

_2.83

_0.00

_0.51

_1.98

7

3

1

_Au

_3.15

_0.13

_0.38

_1.24

TD-CAM-B3LYP

b

1

_Au

_2.62

_0.39

_0.49

_1.14

2

1

_Ag

_2.66

_0.00

_0.22

_1.81

3

1

_Ag

_2.81

_0.00

_0.26

_2.96

4

1

_Ag

_2.83

_0.00

_0.75

_1.71

5

2

1

_Au

_2.87

_0.00

_0.21

_4.25

6

3

1

_Au

_3.06

_0.19

_0.48

_1.22

17

8

1

_Au

_3.83 _0.92

_0.30

_3.91

20

10

1

_Au

_3.97 _0.14

_0.67

_3.56

a

_{SV(P) basis set.;}

b

_{SVP basis set.}

(8)

Table S4. Excited states properties of the lowest four states (dominant contributions and

percentage using NTOs, charge transfer CT and participation ratios PR

NTO

) of circum-1-pyrene

dimer calculated at several computational levels and using Ci symmetry labeling

State. no

State

_{contributions}

Dominant

%

CT

PR

NTO

SOS-ADC(2)

a

1

2

1

_Ag

H-2/L

H/L+2

46

31

0.29

2.76

2

1

_Au

_H/L

₉₃

_0.37

_1.06

3

2

1

_Au

H/L+3

H-3/L

H-2/L+1

H-1/L+2

33

23

21

18

0.26

3.88

4

3

1

_Ag

H-1/L

H/L+1

52

44

0.26

1.98 TD-CAM-B3LYP

b

1

_Au

_{H/ L}

₉₄

_0.49

_1.14

2

1

_Ag

H-1/ L

H/ L+1

70

26

0.22

1.81

3

1

_Ag

_{H/ L+2}

H-2/ L

H-1/ L+3

50

26

12

0.26

2.96

4

1

_Ag

H/ L+1

H-1/ L

72

27

0.75

1.71

5

2

1

_Au

H/ L+3

H-3/ L

H-2/ L+1

H-1/ L+2

31

23

19

0.21

4.25

(9)

Figure S3. Natural Transition Orbitals of coronene monomer (the first row) and dimer (the second

and third row) calculated for the S

1

state at SOS-ADC(2)/def2-TZVP level using Ci symmetry

labeling

Table S5.

Excitation energies, oscillator strengths and CT values for the lowest bright and dark

excited states of the coronene dimer calculated using several computational methods and using Ci

symmetry labeling

State

no.

State

∆E(eV)

f

CT

PR

NTO

(10)

2

1

_Au

_3.25

_0.00

_0.02

_3.93

3

2

1

_Au

_3.73

_0.01

_0.12

_2.90

4

3

1

_Ag

_3.80

_0.00

_0.05

_3.62

5

4

1

_Ag

_4.09

_0.00

_0.35

_2.23

7

3

1

_Au

_4.25

_0.00

_0.24

_4.78

9

4

1

_Au

_4.30

_0.43

_0.56

_2.45

11

5

1

_Au

_4.33

_0.13

_0.18

_4.82

21

10

1

_Au

_4.60

_0.23

_0.78

_2.26

22

11

1

_Au

_4.67

_1.27

_0.12

_3.31

24

12

1

_Au

_4.80

_0.40

_0.29

_3.58

25

13

1

_Au

_4.81

_0.44

_0.28

_3.97

TD-CAM-B3LYP

c

1

2

1

_Ag

_3.50

_0.00

_0.26

_3.57

2

1

_Au

_3.54

_0.00

_0.26

_4.22

3

2

1

_Au

_3.76

_0.00

_0.27

_3.23

4

3

1

_Ag

_3.81

_0.00

_0.26

_4.05

5

4

1

_Ag

_4.20

_0.00

_0.35

_2.13

6

5

1

_Ag

_4.34

_0.00

_0.34

_2.23

7

3

1

_Au

_4.35

_0.24

_0.45

_2.54

9

4

1

_Au

_4.43

_0.02

_0.48

_3.21

10

5

1

_Au

_4.44

_0.03

_0.49

_3.02

21

10

1

_Au

_4.77

_1.23

_0.27

_3.92

22

11

1

_Au

_4.83

_1.03

_0.31

_2.73

a

_{SV(P) basis set;}

b

_{SVP basis set;}

c

_{def2-TZVP basis set.}

Table S6

Excited states properties of the lowest four states and selected higher states (dominant

contributions and percentage using NTOs, charge transfer CT and participation ratios PR

NTO

) of

coronene dimer calculated at several computational levels and using Ci symmetry labeling

State. no

State

_{contributions}

Dominant

%

CT

PR

NTO

(11)

(12)

(13)

10

5

1

_Au

H-2/L+1

H-1/L+3

H/L+2

47

28

18

0.49

3.02

21

10

1

_Au

H-3/L

H-1/L+3

H-2/L+1

H/L+2

38

26

19

12

0.27

3.92

a

_{SV(P) basis set;}

b

_{SVP basis set;}

c

_{def2-TZVP basis set.}

Figure S4.

Natural Transition Orbitals of circum-1-coronene monomer (the first row) and dimer

(the second and third row) calculated for the S

1

state at SOS-ADC(2)/SV(P) level using Ci

symmetry labeling

Table S7 Excited states properties of the lowest four states (dominant contributions and percentage

using NTOs, charge transfer CT and participation ratios PR

NTO

) of circum-1-coronene dimer

calculated at several computational levels and Ci symmetry labeling

State. no

State

Dominant

(14)

3

2

1

_Au

H/L+1

H-1/L

52

42

0.40

2.11

4

3

1

_Ag

H-1/L+1

H/L

58

39

0.50

1.92 TD-CAM-B3LYP

b

1

2

1

_Ag

H/L+1

H-1/L

44

36

0.28

3.02

2

1

_Au

H/L+2

H-2/L

H-3(H-1)/

L+1(L+3)

H-1(H-3)/

L+3(L+1)

28

26

21

0.23

4.38

3

2

1

_Au

H/L

H-1/L+1

46

40

0.29

2.65

4

3

1

_Ag

H-2/L+1

H/L+3

H-1/L+2

H-3/L

31

24

22

19

0.22

4.15

18

9

1

_Au

H-1(H-3)/

L+3(L+1,

L+5)

H-3/L+1

H-2/L

H/L+2

30

29

19

18

0.24

4.34

a

_{SV(P) basis set;}

b

_{SVP basis set.}

Table S8

.

Excitation energies, oscillator strengths and CT values for the lowest bright and dark

excited states of the circum-1-coronene dimer calculated using several computational levels and

Ci symmetry labeling

State no.

State

∆E(eV)

f

CT

PR

NTO

SOS-ADC(2)

a

1

2

1

_Ag

_2.17

_0.00

_0.21

_2.43

2

1

_Au

_2.30

_0.00

_0.06

_3.94

3

2

1

_Au

_2.50

_0.03

_0.40

_2.11

4

3

1

_Ag

_2.64

_0.00

_0.50

_1.92

5

4

1

_Ag

_2.70

_0.00

_0.09

_3.40

6

3

1

_Au

_2.82

_0.66

_0.73

_2.26

TD-CAM-B3LYP

b

1

2

1

_Ag

_2.52

_0.00

_0.28

_3.02

2

1

_Au

_2.60

_0.00

_0.23

_4.38

3

2

1

_Au

_2.69

_0.01

_0.29

_2.65

4

3

1

_Ag

_2.79

_0.00

_0.22

_4.15

5

4

1

_Ag

_2.93

_0.00

_0.45

_2.05

6

3

1

_Au

_3.06

_0.30

_0.56

_2.77

18

9

1

_Au

_3.57

_1.69

_0.24

_4.34

(15)

Figure S5. Definition of x and y for pyrene and coronene dimer structures of a) pyrene and b)

coronene

Table S9. Adiabatic energy (in eV) comparison for different S1 optimized pyrene dimer

calculated at SOS-ADC(2)/SV(P) level

a

Symmetry

C2h

b

_Ci

c

Label

Ag

Bg

Ag

Au

Initial

displacement

x 0.0, y 0.4

3.46

3.49 x 0.3

x 1.0

3.47

3.48

3.47

3.96 x 2.3

3.90

3.46

3.90

3.96

a

_{reference energy is ground state minimum as shown in Figure 1, total energy = -1226.32229}

Hartree. Definition of x and y see Figure S5;

b

_{Unless specified, y=0.0Å;}

c

_{Unless specified, y=0.2Å}

Table S10. Adiabatic energy (in eV) comparison for different S1 optimized coronene dimer

calculated at SOS-ADC(2)/SV(P) level

a

Symmetry

C2h

b

_Ci

c

Label

Ag

Bg

Ag

Au

Initial

displacement

x 0.0, y 0.4

3.21 x 0.3

x 1.0

3.58

3.10

3.68 x 2.3

3.81

3.09

3.20

a

_{reference energy is ground state minimum as shown in Figure 1, total energy = -1836.08180}

(16)

Cartesian geometries (Å)

C

i

symmetry: 1

1

Ag

(17)

H 0.1017117 5.4479571 1.5411455 H -2.0539556 4.2315253 1.6641358 H 2.2041769 -2.5440338 1.6600008 H 0.0480255 -3.7612574 1.7648354 H -2.0933322 -2.5151199 1.8218528

C

i

symmetry: 1

1

Ag

(18)

(19)

C 0.0570156 5.7699368 1.5199509 C -1.1942093 6.4679843 1.5337604 C -2.3911342 5.7852632 1.5931515 C 2.5061123 5.7670552 1.4927841 C 1.3128533 6.4586427 1.4824552 H 4.6988131 4.1503978 1.5079418 H 5.9466246 1.9958363 1.5365330 H 5.9375610 -0.4795152 1.5529711 H 4.6758226 -2.6255357 1.5721750 H 3.4214113 -4.7796525 1.6482810 H 1.2677045 -6.0065990 1.7341618 H -1.2312205 -5.9974453 1.7846294 H -3.3775374 -4.7547153 1.7864922 H -4.6181057 -2.5912238 1.7623063 H -5.8549576 2.0395969 1.7783863 H -5.8636200 -0.4357719 1.7947353 H -4.5933501 4.1849492 1.6984869 H -1.1874454 7.5672143 1.5341943 H -3.3405566 6.3386656 1.6187664 H 3.4599149 6.3133271 1.4795339 H 1.3143414 7.5579147 1.4831495

C

i

symmetry: 1

1

Ag

(20)

H -4.1639335 -3.4597576 -1.4849699 H -2.0059010 -4.6941461 -1.5469263 H 0.4591068 -4.6826790 -1.6183062 H 2.6055160 -3.4310452 -1.6856772 H 3.8280797 -1.2909517 -1.7630451 H 3.8165470 1.1932388 -1.8153318 H 2.5738995 3.3229961 -1.8328868 H 0.4153150 4.5556686 -1.8256878 H -2.0499923 4.5466449 -1.7568748 C -2.7303733 -1.1924518 1.7807955 C -2.7419998 1.2987222 1.7270077 C -0.6145869 -2.3994856 1.7437005 C -0.6311082 0.0613284 1.6698948 C -0.6379279 2.5229594 1.6335536 C 1.4991825 -3.6096673 1.7319318 C 1.5134556 -1.1648240 1.6375190 C 1.5017805 1.3051930 1.5812000 C 1.4640768 3.7517439 1.5643663 C 3.6506224 -2.3557548 1.6181533 C 3.6362216 0.0788436 1.5384084 C 3.6273519 2.5145433 1.5069734 C -2.0380211 -2.3782588 1.7888872 C -2.0472447 0.0557461 1.7204212 C -2.0607822 2.4903185 1.6821090 C 0.1264649 -3.6150473 1.7702473 C 0.0875028 -1.1707750 1.6713669 C 0.0757433 1.2989572 1.6156133 C 0.0915824 3.7456395 1.6041918 C 2.2273438 -2.3880917 1.6579316 C 2.2200544 0.0728007 1.5731830 C 2.2039679 2.5348860 1.5453479 C 4.3311327 -1.1649489 1.5527874 C 4.3192307 1.3284177 1.4960407 H -2.6055160 3.4310452 1.6856772 H -3.8280797 1.2909517 1.7630451 H -3.8165470 -1.1932388 1.8153318 H -2.5738995 -3.3229961 1.8328868 H -0.4153150 -4.5556686 1.8256878 H 2.0499923 -4.5466449 1.7568748 H 4.1962030 -3.2958481 1.6383932 H 5.4178925 -1.1575239 1.5263901 H 5.4060015 1.3302120 1.4702H-1 H 4.1639335 3.4597576 1.4849699 H 2.0059010 4.6941461 1.5469263 H -0.4591068 4.6826790 1.6183062

C

i

symmetry: 1

1

Ag

Geometry optimization of ground state at MP2/SV(P) level

Circum-1-coronene dimer

(21)

(22)

(23)

C -2.1052611 4.9425768 1.5626824 C 0.0912909 -6.1533717 1.7378409 C 0.0524336 -3.6845385 1.6244592 C 0.0464665 -1.2106044 1.5646407 C 0.0379309 1.2578563 1.5277541 C 0.0268147 3.7324656 1.5137792 C 0.0485963 6.2038336 1.5537452 C 2.2086290 -4.9137477 1.6685128 C 2.1921796 -2.4436188 1.5647559 C 2.1799580 0.0304430 1.5073296 C 2.1750620 2.5051429 1.4907982 C 2.1744176 4.9773438 1.5209251 C 4.3337262 -3.6782881 1.6039815 C 4.3282541 -1.1976444 1.5032365 C 4.3197007 1.2727274 1.4661863 C 4.3079546 3.7552478 1.4926784 C 6.4589447 -2.4514514 1.5405111 C 6.4422554 0.0446122 1.4659685 C 6.4416292 2.5418453 1.4654876 H -4.8154735 4.6452777 1.6484585 H -2.6580594 5.8933978 1.5824218 H -0.5069721 7.1516382 1.5750261 H 1.9701813 7.1600355 1.5668590 H 4.1291092 5.9150834 1.5369746 H 6.2952497 4.6825543 1.5001582 H 7.5408716 2.5433534 1.4657982 H 7.5425510 0.0484425 1.4678161 H 7.5581697 -2.4452726 1.5408700 H 6.3274779 -4.5910931 1.6394063 H 4.1698408 -5.8370078 1.7125186 H 2.0194181 -7.0954755 1.7792255 H -0.4576752 -7.1039878 1.7872490 H -2.6175634 -5.8609088 1.7577843 H -4.7836138 -4.6262002 1.7875391 H -6.0281609 -2.4859903 1.7949674 H -6.0303092 0.0058698 1.7589382 H -6.0453194 2.4977264 1.7199015

C

2h

symmetry: 2

1

Ag

Geometry optimization of S

1

state at SOS-ADC(2)/SV(P) level

Pyrene dimer, ADC(2)-1

(24)

C -0.3611719 1.6386853 3.5454500 C -1.5846293 1.6933235 2.8486233 C 0.8572390 1.5595115 -2.8486285 C -0.3611719 1.6386853 -3.5454500 C -1.5846293 1.6933235 -2.8486233 H -3.7866452 1.8524421 1.2400800 H -3.7866452 1.8524421 -1.2400800 H 3.0524107 1.4102414 1.2396045 H 3.0524107 1.4102414 -1.2396045 H 1.8059683 1.5268236 3.4007160 H -0.3603648 1.6627209 4.6434817 H -2.5302252 1.7629724 3.4042899 H 1.8059683 1.5268236 -3.4007160 H -0.3603648 1.6627209 -4.6434817 H -2.5302252 1.7629724 -3.4042899 C 0.3683322 -1.5942681 0.7068274 C 0.3683322 -1.5942681 -0.7068274 C -0.8795525 -1.5323475 1.4344371 C -0.8795525 -1.5323475 -1.4344371 C -2.1022771 -1.4593798 0.6902125 C -2.1022771 -1.4593798 -0.6902125 C 2.8383883 -1.7737213 0.6897457 C 2.8383883 -1.7737213 -0.6897457 C 1.6143003 -1.6780208 1.4360054 C 1.6143003 -1.6780208 -1.4360054 C 1.5846293 -1.6933235 2.8486233 C 0.3611719 -1.6386853 3.5454500 C -0.8572390 -1.5595115 2.8486285 C 1.5846293 -1.6933235 -2.8486233 C 0.3611719 -1.6386853 -3.5454500 C -0.8572390 -1.5595115 -2.8486285 H -3.0524107 -1.4102414 1.2396045 H -3.0524107 -1.4102414 -1.2396045 H 3.7866452 -1.8524421 1.2400800 H 3.7866452 -1.8524421 -1.2400800 H 2.5302252 -1.7629724 3.4042899 H 0.3603648 -1.6627209 4.6434817 H -1.8059683 -1.5268236 3.4007160 H 2.5302252 -1.7629724 -3.4042899 H 0.3603648 -1.6627209 -4.6434817 H -1.8059683 -1.5268236 -3.4007160

C

i

symmetry: 2

1

Ag

Geometry optimization of S

1

state at SOS-ADC(2)/SV(P) level

(25)

C 2.3837584 -0.9501916 -1.5923092 C 1.1647684 1.1754337 -1.6860452 C 1.1685856 -1.6835980 -1.5160991 C 1.1390730 2.6042339 -1.7069009 C -0.0788837 3.2917672 -1.7686816 C -1.2930164 2.6036838 -1.6908434 C 1.1445352 -3.1103093 -1.4259760 C -0.0703593 -3.8015637 -1.3828280 C -1.2870970 -3.1100142 -1.3769923 H -3.4878946 0.9832131 -1.6226789 H -3.4871904 -1.4971743 -1.4832046 H 3.3340236 0.9868403 -1.6884174 H 3.3383406 -1.4946805 -1.5681606 H 2.0888026 3.1533169 -1.7679427 H -0.0801457 4.3894920 -1.8099003 H -2.2442539 3.1525075 -1.7330807 H 2.0957678 -3.6601641 -1.4257657 H -0.0693763 -4.8983916 -1.3195202 H -2.2373241 -3.6603530 -1.3367583 C 0.0753881 0.9698515 1.5831969 C 0.0765692 -0.4576695 1.6102389 C -1.1685856 1.6835980 1.5160991 C -1.1647684 -1.1754337 1.6860452 C -2.3837584 0.9501916 1.5923092 C -2.3812281 -0.4407400 1.6421069 C 2.5337811 0.9522685 1.5310935 C 2.5333143 -0.4386931 1.5926500 C 1.3160136 1.6845751 1.4794223 C 1.3193789 -1.1740645 1.6630204 C 1.2870970 3.1100142 1.3769923 C 0.0703593 3.8015637 1.3828280 C -1.1445352 3.1103093 1.4259760 C 1.2930164 -2.6036838 1.6908434 C 0.0788837 -3.2917672 1.7686816 C -1.1390730 -2.6042339 1.7069009 H -3.3383406 1.4946805 1.5681606 H -3.3340236 -0.9868403 1.6884174 H 3.4871904 1.4971743 1.4832046 H 3.4878946 -0.9832131 1.6226789 H 2.2373241 3.6603530 1.3367583 H 0.0693763 4.8983916 1.3195202 H -2.0957678 3.6601641 1.4257657 H 2.2442539 -3.1525075 1.7330807 H 0.0801457 -4.3894920 1.8099003 H -2.0888026 -3.1533169 1.7679427

C

2h

symmetry: 1

1

Bg

Geometry optimization of S

1

state at SOS-ADC(2)/SV(P) level

Pyrene dimer, ADC(2)-3

(26)

C -2.5728598 -1.4913898 -1.2494830 C -0.4495079 -1.5238024 -2.4786697 C -1.8285525 -1.5200572 -2.4776145 C -0.4495079 -1.5238024 2.4786697 C -1.8285525 -1.5200572 2.4776145 C 0.2957830 -1.5389000 1.2507429 C -2.5728598 -1.4913898 1.2494830 C 1.7085725 -1.5574623 1.2257920 C 2.4019142 -1.5810559 0.0000000 C 1.7085725 -1.5574623 -1.2257920 C -3.9876262 -1.5162871 1.2231695 C -4.6808622 -1.5113730 0.0000000 C -3.9876262 -1.5162871 -1.2231695 H 0.1027742 -1.5520673 -3.4278497 H -2.3812886 -1.5236523 -3.4278341 H 0.1027742 -1.5520673 3.4278497 H -2.3812886 -1.5236523 3.4278341 H 2.2643423 -1.5889019 2.1719323 H 3.4999781 -1.5913900 0.0000000 H 2.2643423 -1.5889019 -2.1719323 H -4.5429332 -1.5182090 2.1712214 H -5.7793047 -1.5279289 -0.0000000 H -4.5429332 -1.5182090 -2.1712214 C 1.8458601 1.5229787 0.0000000 C 0.4299885 1.4906928 0.0000000 C 2.5728598 1.4913898 -1.2494830 C -0.2957830 1.5389000 -1.2507429 C 1.8285525 1.5200572 -2.4776145 C 0.4495079 1.5238024 -2.4786697 C 1.8285525 1.5200572 2.4776145 C 0.4495079 1.5238024 2.4786697 C 2.5728598 1.4913898 1.2494830 C -0.2957830 1.5389000 1.2507429 C 3.9876262 1.5162871 1.2231695 C 4.6808622 1.5113730 -0.0000000 C 3.9876262 1.5162871 -1.2231695 C -1.7085725 1.5574623 1.2257920 C -2.4019142 1.5810559 0.0000000 C -1.7085725 1.5574623 -1.2257920 H 2.3812886 1.5236523 -3.4278341 H -0.1027742 1.5520673 -3.4278497 H 2.3812886 1.5236523 3.4278341 H -0.1027742 1.5520673 3.4278497 H 4.5429332 1.5182090 2.1712214 H 5.7793047 1.5279289 0.0000000 H 4.5429332 1.5182090 -2.1712214 H -2.2643423 1.5889019 2.1719323 H -3.4999781 1.5913900 0.0000000 H -2.2643423 1.5889019 -2.1719323

C

i

symmetry: 2

1

Ag

(27)

(28)

(29)

H 5.9107674 -0.7507530 1.5980950 H 4.6620688 -2.9079919 1.5726622 H 3.4139776 -5.0665712 1.6058076 H 1.2615967 -6.2955172 1.6564279 H -1.2355129 -6.2915468 1.6889080 H -3.3844361 -5.0556710 1.6955922 H -4.6260115 -2.8930994 1.6991819 H -5.8635161 1.7466524 1.7565997 H -5.8664992 -0.7319212 1.7605980 H -4.6145960 3.9009934 1.6741978 H -1.2H-1804 7.2938865 1.6309924 H -3.3674433 6.0616005 1.6536296 H 3.4314079 6.0506839 1.5647368 H 1.2837264 7.2898410 1.5993771

C

2h

symmetry: 2

1

Ag

Geometry optimization of S

1

state at SOS-ADC(2)/SV(P) level

Coronene dimer, ADC(2)-1

(30)

H 4.2691225 -1.4723297 1.2431168 H 4.2691225 -1.4723297 -1.2431168 C -0.8715144 1.6218075 -3.5509837 C 1.6263615 1.7090201 -3.5505890 C -2.0994784 1.5467625 -1.4313355 C 0.3814016 1.6419260 -1.4272555 C 2.8607379 1.7240987 -1.4330364 C -3.3172486 1.4951648 0.6947825 C -0.8526875 1.5595175 0.7138013 C 1.6176360 1.6504819 0.7140842 C 4.0822038 1.7775341 0.6930416 C -2.0711568 1.5559076 2.8593818 C 0.3802071 1.6287874 2.8646538 C 2.8305666 1.7357682 2.8578875 C -2.0711568 1.5559076 -2.8593818 C 0.3802071 1.6287874 -2.8646538 C 2.8305666 1.7357682 -2.8578875 C -3.3172486 1.4951648 -0.6947825 C -0.8526875 1.5595175 -0.7138013 C 1.6176360 1.6504819 -0.7140842 C 4.0822038 1.7775341 -0.6930416 C -2.0994784 1.5467625 1.4313355 C 0.3814016 1.6419260 1.4272555 C 2.8607379 1.7240987 1.4330364 C -0.8715144 1.6218075 3.5509837 C 1.6263615 1.7090201 3.5505890 H 3.7793295 1.7942073 -3.4097486 H 1.6276849 1.7248563 -4.6497505 H -0.8725902 1.6342026 -4.6502189 H -3.0227239 1.5451692 -3.4084193 H -4.2691225 1.4723297 -1.2431168 H -4.2691225 1.4723297 1.2431168 H -3.0227239 1.5451692 3.4084193 H -0.8725902 1.6342026 4.6502189 H 1.6276849 1.7248563 4.6497505 H 3.7793295 1.7942073 3.4097486 H 5.0327862 1.8313173 1.2422203 H 5.0327862 1.8313173 -1.2422203

C

i

symmetry: 2

1

Ag

Geometry optimization of S

1

state at SOS-ADC(2)/SV(P) level

Coronene dimer, ADC(2)-2

(31)

(32)

H -4.4259258 -0.8871097 1.5191183 H -3.1916056 -3.0421171 1.4132491 H -1.0325641 -4.2983806 1.3731340 H 1.4532486 -4.3073864 1.4161876 H 3.6212255 -3.0712804 1.5527062 H 4.8720558 -0.9293318 1.6966831 H 4.8818743 1.5714832 1.8042448 H 3.6489720 3.7273943 1.8751843 H 1.4851857 4.9863867 1.9120414 H -0.9993332 4.9936803 1.9002372

C

i

symmetry: 2

1

Ag

Geometry optimization of S

1

state at SOS-ADC(2)/SV(P) level

Coronene dimer, ADC(2)-3

(33)

C -0.9282810 -2.4500347 1.6740650 C -0.9275100 0.0285829 1.6192658 C -0.9403435 2.5076878 1.5894088 C 1.2010414 -3.6653583 1.7009480 C 1.2158595 -1.2020881 1.6246574 C 1.2097257 1.2695581 1.5823713 C 1.1828693 3.7340374 1.5759430 C 3.3629985 -2.4115938 1.6401285 C 3.3638998 0.0385496 1.5718276 C 3.3508833 2.4896086 1.5554258 C -2.3534139 -2.4241895 1.6731850 C -2.3664754 0.0246976 1.6104104 C -2.3653696 2.4743617 1.5896634 C -0.1866806 -3.6687938 1.6950959 C -0.2112408 -1.2063238 1.5941969 C -0.2173331 1.2655647 1.5520476 C -0.2049319 3.7301902 1.5694840 C 1.9366202 -2.4457301 1.6259261 C 1.9253061 0.0345178 1.5474286 C 1.9242746 2.5161687 1.5414591 C 4.0553553 -1.2101124 1.5877575 C 4.0490640 1.2905499 1.5432657 H -2.9172866 3.4248646 1.5997404 H -4.1562443 1.2702152 1.6381864 H -4.1503019 -1.2278273 1.6797014 H -2.9005252 -3.3766217 1.7151651 H -0.7327912 -4.6210953 1.7462663 H 1.7517509 -4.6163424 1.7304145 H 3.9160149 -3.3612239 1.6675137 H 5.1545193 -1.2079947 1.5968787 H 5.1482176 1.2941562 1.5504698 H 3.8991500 3.4423493 1.5503109 H 1.7287936 4.6883101 1.5740508 H -0.7558757 4.6809010 1.5880742

C

i

symmetry: 2

1

Ag

Geometry optimization of S

1

state at SOS-ADC(2)/SV(P) level

Coronene dimer, ADC(2)-4

(34)

(35)

H 4.5139769 -3.3550566 1.5397748 H 5.7418970 -1.1968396 1.4736036 H 5.7280405 1.3065150 1.4340834 H 4.4762661 3.4519904 1.4318456 H 2.3040436 4.6907731 1.4545270 H -0.1839169 4.6772287 1.5048584

C

i

symmetry: 2

1

Ag

Geometry optimization of S

1

state at SOS-ADC(2)/SV(P) level

Circum-1-coronene dimer, ADC(2)-1

(36)

(37)

(38)

Geometry optimization of S

1

state at SOS-ADC(2)/SV(P) level

Circum-1-coronene dimer, ADC(2)-2

(39)

(40)

Supplementary Information for