Supporting Information – Unveiling the

Ionization Energy of the CN Radical

Bérenger Gans,∗,† Séverine Boyé-Péronne,† Gustavo A. Garcia,‡ Anja Röder,¶

Domenik Schleier,¶ Philippe Halvick,§ and Jean-Christophe Loison∗,§

†Institut des Sciences Moléculaires d’Orsay (ISMO), CNRS, Univ. Paris-Sud, Université
Paris-Saclay, F-91405 Orsay, France
‡Synchrotron SOLEIL, L’Orme des Merisiers, Saint Aubin BP 48, F-91192 Gif sur Yvette
Cedex, France
¶Institute of Physical and Theoretical Chemistry, University of Würzburg, Am Hubland,
D-97074 Würzburg, Germany
§Institut des Sciences Moléculaires, UMR 5255 CNRS–Université de Bordeaux, Bât. A12,
351 cours de la Libération, F-33405 Talence Cedex, France

E-mail: berenger.gans@u-psud.fr; jean-christophe.loison@u-bordeaux.fr

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Table SI: MRCI Calculated equilibrium properties of neutral and cationic CN radical (dis-
tances in Å and energies in hartrees).

Basis set Re Ecalc.

X 2 Σ+ CN AVTZ 1.1799 −92.57439166
AVQZ 1.1759 −92.59476662
AV5Z 1.1748 −92.60087284
AV6Z 1.1745 −92.60297811
CBS(AVnZ) = −92.60377
X+ 1 Σ+ CN+ AVTZ 1.1812 −92.06644862
AVQZ 1.1771 −92.08496282
AV5Z 1.1761 −92.09038055
AV6Z 1.1757 −92.09218461
CBS(AVnZ) = −92.09284

a+ 3 Π CN+ AVTZ 1.2518 −92.06432354

AVQZ 1.2471 −92.08211851
AV5Z 1.2459 −92.08733626
AV6Z 1.2455 −92.08908311
CBS(AVnZ) = −92.08972

A+ 1 Π CN+ AVTZ 1.2568 −92.03028807

AVQZ 1.2522 −92.04846213
AV5Z 1.2510 −92.05383055
AV6Z 1.2506 −92.05564253
CBS(AVnZ) = −92.05631

b+ 3 Σ− CN+ AVTZ 1.3668 −92.02841217

AVQZ 1.3619 −92.04513356
AV5Z 1.3608 −92.05009432
AV6Z 1.3604 −92.05176170
CBS(AVnZ) = −92.05239

c+ 3 Σ+ CN+ AVTZ 1.1466 −92.01624546

AVQZ 1.1425 −92.03540199
AV5Z 1.1414 −92.04099752
AV6Z 1.1410 −92.04283975
CBS(AVnZ) = −92.04352

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Table SII: Calculated Franck-Condon factors of the A+ 1 Π ← X 2 Σ+ ionizing transition of
CN.

v+
0 1 2 3 4 5 6
v
0 0.350 0.336 0.188 0.081 0.030 0.010 0.003
1 0.391 0.001 0.122 0.197 0.149 0.081 0.036
2 0.192 0.197 0.112 0.003 0.098 0.146 0.118
3 0.055 0.280 0.028 0.164 0.030 0.016 0.090
4 0.010 0.140 0.233 0.007 0.109 0.092 0.003
5 0.001 0.038 0.211 0.125 0.067 0.032 0.111
6 0.000 0.007 0.084 0.236 0.034 0.120 0.000

Table SIII: Calculated Franck-Condon factors of the c+ 1 Σ+ ← X 2 Σ+ ionizing transition of

CN.

v+
0 1 2 3 4 5 6
v
0 0.790 0.194 0.016 0.000 0.000 0.000 0.000
1 0.179 0.464 0.313 0.042 0.002 0.000 0.000
2 0.027 0.263 0.253 0.380 0.073 0.003 0.000
3 0.004 0.066 0.285 0.125 0.411 0.105 0.005
4 0.000 0.012 0.103 0.269 0.053 0.421 0.136
5 0.000 0.002 0.024 0.133 0.234 0.017 0.420
6 0.000 0.000 0.005 0.039 0.153 0.192 0.003