Table A.1: Adiabatic and vertical ionisation energies (in eV) of each PAH in our sample evaluated at the B3LYP/6-31+G$^\star $ level of theory. Whenever available, we list laboratory data for comparison. The experimental single IEs come from the NIST Chemistry WebBook (Lias 2005) while second and double IEs are, respectively, from charge stripping and photon-impact measurements of Schröder et al. (2001) for corannulene and coronene and from Tobita et al. (1994) in all the other cases. According to our calculations the dication electronic ground-states are marked in boldface.
PAH First IE (I+) Dication Second IE ($\Delta I$) Double IE (I++)    
molecule Adiab. Vert. Exp. state Adiab. Vert. Exp. Adiab. Vert. Exp. $I^+_{\rm V} + \Delta I_{\rm V}$ $I^{++}_{\rm V}$ - ( $I^+_{\rm V} + \Delta I_{\rm V}$)
Azulene 7.15 7.27 7.42 $\pm$ 0.02 singlet 12.77 12.87 - 19.92 20.34 - 20.14 + 0.20
(C10H8) triplet 13.39 13.53 20.54 20.63 20.80 - 0.17
Naphthalene 7.80 7.89 8.144 $\pm$ 0.001 singlet 13.19 13.28 14.6 $\pm$ 0.5 20.99 21.35 21.5 $\pm$ 0.2 21.17 + 0.18
(C10H8) triplet 13.65 13.77 21.45 21.57 21.66 - 0.09
Acenaphtylene 7.66 7.86 8.12 $\pm$ 0.10 singlet 12.81 13.06 - 20.48 21.32 21.4 $\pm$ 0.2 20.92 + 0.39
(C12H8) triplet 12.78 12.88 20.45 20.66 20.74 - 0.08
Biphenylene 7.22 7.37 7.58 $\pm$ 0.03 singlet 12.09 12.26 - 19.31 19.94 19.7 $\pm$ 0.2 19.63 + 0.31
(C12H8) triplet 13.23 13.31 20.45 20.61 20.68 - 0.08
Acenaphthene 7.37 7.46 7.75 $\pm$ 0.05 singlet 12.42 12.51 - 19.78 20.17 21.7 $\pm$ 0.2 19.97 + 0.20
(C12H10) triplet 13.22 13.35 20.59 20.72 20.81 - 0.09
Fluorene 7.56 7.69 7.91 $\pm$ 0.02 singlet 12.39 12.52 - 19.96 20.47 21.0 $\pm$ 0.2 20.22 + 0.26
(C13H10) triplet 12.86 12.99 20.43 20.59 20.68 - 0.09
Anthracene 7.02 7.09 7.439 $\pm$ 0.006 singlet 11.68 11.74 - 18.70 18.95 - 18.83 + 0.12
(C14H10) triplet 12.68 12.77 19.70 19.80 19.86 - 0.06
Phenanthrene 7.53 7.63 7.891 $\pm$ 0.001 singlet 12.11 12.23 - 19.63 20.08 - 19.86 + 0.22
(C14H10) triplet 12.19 12.32 19.72 19.86 19.96 - 0.09
Pyrene 7.07 7.14 7.426 $\pm$ 0.001 singlet 11.57 11.64 14.4 $\pm$ 0.5 18.63 18.92 19.8 $\pm$ 0.2 18.78 + 0.14
(C16H10) triplet 12.28 12.39 19.35 19.44 19.53 - 0.09
Tetracene 6.49 6.55 6.97 $\pm$ 0.05 singlet 10.66 10.70 13.1 $\pm$ 0.5 17.15 17.34 18.6 $\pm$ 0.2 17.25 + 0.09
(C18H12) triplet 11.47 11.55 17.96 18.11 18.10 + 0.01
Chrysene 7.17 7.25 7.60 $\pm$ 0.01 singlet 11.28 11.37 - 18.45 18.78 - 18.63 + 0.16
(C18H12) triplet 11.67 11.75 18.84 18.94 19.01 - 0.06
Benz[a]anthracene 6.98 7.05 7.45 $\pm$  0.05 singlet 11.16 11.24 - 18.14 18.42 - 18.29 + 0.13
(C18H12) triplet 11.35 11.45 18.33 18.48 18.50 - 0.02
Triphenylene 7.52 7.86 7.87 $\pm$ 0.02 singlet 11.72 11.81 - 19.24 19.59 - 19.67 - 0.08
(C18H12) triplet 11.57 11.65 19.09 19.20 19.51 - 0.31
Corannulene 7.62 7.73 7.83 $\pm$ 0.02 singlet 12.02 12.15 13.8 $\pm$ 0.3 19.63 20.14 20.1 $\pm$ 0.2 19.88 + 0.26
(C20H10) triplet 11.66 11.76 19.28 19.50 19.49 + 0.01
Benzo[a]pyrene 6.71 6.78 7.12 $\pm$ 0.01 singlet 10.75 10.82 - 17.46 17.73 - 17.60 +0.13
(C20H12) triplet 11.47 11.58 18.18 18.30 18.36 -0.06
Benzo[e]pyrene 7.05 7.12 7.43 $\pm$ 0.04 singlet 11.20 11.26 - 18.25 18.51 - 18.38 + 0.13
(C20H12) triplet 11.34 11.42 18.38 18.52 18.54 -0.02
Perylene 6.57 6.64 6.960 $\pm$ 0.001 singlet 10.62 10.68 - 17.19 17.46 18.0 $\pm$ 0.2 17.33 + 0.14
(C20H12) triplet 12.03 12.11 18.60 18.73 18.75 -0.02
Anthanthrene 6.46 6.52 6.92 $\pm$ 0.04 singlet 10.43 10.48 - 16.90 17.10 - 17.00 + 0.10
(C22H12) triplet 11.38 11.54 18.01 18.09 18.06 +0.03
Benzo[g,h,i]perylene 6.79 6.86 7.17 $\pm$ 0.02 singlet 10.74 10.80 - 17.53 17.78 - 17.65 + 0.13
(C22H12) triplet 11.19 11.28 17.98 18.09 18.14 - 0.05
Pentacene 6.12 6.16 6.63 $\pm$ 0.05 singlet 9.91 9.94 12.8 $\pm$ 0.5 16.03 16.18 17.4 $\pm$ 0.2 16.11 + 0.07
(C22H14) triplet 10.56 10.63 16.67 16.79 16.79 0.00
Coronene 7.02 7.08 7.29 $\pm$ 0.03 singlet 10.87 10.92 12.8 $\pm$ 0.3 17.88 18.11 18.5 $\pm$ 0.2 18.00 + 0.11
(C24H12) triplet 10.72 10.79 17.74 17.80 17.87 -0.06
Dibenzo[b,def]crysene 6.39 6.45 6.82 singlet 10.11 10.17 - 16.50 16.73 - 16.62 + 0.11
(C24H14)     triplet 11.00 11.06  17.39 17.51  17.51 0.00
Dibenzo[cd,lm]perylene 6.31 6.38 6.72 $\pm$ 0.02 singlet 9.88 9.94 - 16.20 16.45 - 16.32 + 0.13
(C26H14) triplet 11.03 11.12 17.35 17.43 17.50 - 0.07
Hexacene 5.83 5.87 6.36 $\pm$ 0.02 singlet 9.34 9.37 - 15.18 15.30 - 15.24 +0.06
(C26H16) triplet 9.84 9.90 15.68 15.78 15.78 0.00
Bisanthene 5.85 5.90 6.30 singlet 9.47 9.51 - 15.33 15.48 - 15.40 + 0.08
(C28H14) triplet 10.69 10.76 16.54 16.70 16.66 + 0.04
Benzo[a]coronene 6.75 6.81 7.08 singlet 10.34 10.39 - 17.10 17.30 - 17.20 + 0.10
(C28H14) triplet 10.46 10.52 17.21 17.29 17.33 - 0.04
Dibenzo[bc,kl]coronene 6.01 6.05 6.42 $\pm$ 0.02 singlet 9.54 9.57 - 15.55 15.70 - 15.62 + 0.08
(C30H14) triplet 10.19 10.27 16.20 16.36 16.32 + 0.04
Dibenzo[bc,ef]coronene 6.12 6.17 6.50 singlet 9.66 9.69 - 15.78 15.94 - 15.86 + 0.08
(C30H14) triplet 10.67 10.78 16.79 16.87 16.95 -0.08
Terrylene 5.98 6.05 6.42 $\pm$ 0.02 singlet 9.33 9.38 - 15.31 15.55 - 15.43 + 0.12
(C30H16) triplet 10.40 10.45 16.38 16.49 16.50 - 0.01
Ovalene 6.36 6.41 6.71 singlet 9.82 9.86 - 16.18 16.34 - 16.26 + 0.08
(C32H14) triplet 10.30 10.35 16.66 16.72 16.76 -0.04
Tetrabenzo[bc,ef,kl,no]coronene 5.41 5.44 - singlet 8.75 8.77 - 14.16 14.24 - 14.21 + 0.03
(C36H16) triplet 9.66 9.72 15.07 15.17 15.15 + 0.02
Circumbiphenyl 6.46 6.52 6.81 $\pm$ 0.02 singlet 9.58 9.64 - 16.04 16.26 - 16.15 + 0.11
(C38H16) triplet 9.70 9.75 16.16 16.21 16.27 -0.06
Circumanthracene 5.90 5.94 - singlet 9.10 9.13 - 15.00 15.12 - 15.06 + 0.06
(C40H16) triplet 9.76 9.82 15.66 15.95 15.75 + 0.20
Quaterrylene 5.62 5.68 6.11 $\pm$ 0.02 singlet 8.50 8.55 - 14.12 14.35 - 14.23 + 0.12
(C40H20) triplet 9.36 9.40 14.97 15.08 15.08 0.00
Circumpyrene 6.06 6.10 - singlet 9.13 9.16 - 15.19 15.35 - 15.27 + 0.08
(C42H16) triplet 9.68 9.73 15.75 15.80 15.84 -0.04
Hexabenzocoronene 6.55 6.79 - singlet 9.58 9.63 - 16.14 16.33 - 16.42 -0.09
(C42H18) triplet 9.52 9.57 16.07 16.15 16.36 -0.21
Dicoronylene 6.07 6.13 - singlet 8.84 8.89 - 14.91 15.13 - 15.02 + 0.11
(C48H20) triplet 9.37 9.40 15.44 15.50 15.53 -0.03
Pentarylene 5.37 5.43 - singlet 7.92 7.97 - 13.29 13.51 - 13.39 + 0.11
(C50H24) triplet 8.64 8.68 14.00 14.10 14.11 - 0.01
Circumcoronene 6.14 6.35 - singlet 8.90 9.04 - 15.05 15.19 - 15.28 -0.09
(C54H18) triplet 8.81 8.85 14.95 15.00 15.19 -0.19
Circumovalene 5.71 5.74 - singlet 8.32 8.34 - 14.02 14.12 - 14.07 +0.05
(C66H20) triplet 8.67 8.70 14.37 14.42 14.44 - 0.02

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