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Vibronic structure of the 2Piu ground electronic state of dicyanoacetylene cation revisited by PFI- ZEKE photoelectron spectroscopy and ab initio calculations

par Lamarre, Nicolas;Gans, Bérenger;Alcaraz, Christian;Cunha de Miranda, Barbara;Guillemin, Jean-Claude;Broquier, Michel;Liévin, Jacques ;Boyé-Péronne, Séverine
Référence Molecular Physics, 113, page (3946-3954)
Publication Publié, 2015

Article révisé par les pairs

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Résumé :

The X+2Πu ← X1Σ+g transition of dicyanoacetylene has been recorded for the first time using pulsed-field-ionisation zero-kinetic-energy photoelectron spectroscopy. The analysis of the photoelectron spectrum allowed an accurate determination of the adiabatic ionisation potential of C4N2 (Ei, ad./hc = 95,479 ± 2 cm-1) and a description of the vibrational structure of the electronic ground state of the cation which is affected by the Renner-Teller effect and the spin-orbit interaction. The spin-orbit coupling constant was measured as -52 ± 2 cm-1. These results are supported by ab initio calculations performed at the complete active space self-consistent field and second-order perturbation theory levels of theory, with extrapolation to the complete basis set limit.