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Experimental and ab initio characterization of HC3N+ vibronic structure. II. High-resolution VUV PFI-ZEKE spectroscopy

par Gans, Bérenger;Lamarre, Nicolas;Broquier, Michel;Liévin, Jacques ;Boyé-Péronne, Séverine
Référence The Journal of Chemical Physics, 145, 23, 234309
Publication Publié, 2016-12

Article révisé par les pairs

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Résumé :

Vacuum-ultraviolet pulsed-field-ionization zero-kinetic-energy photoelectron spectra of X+Π2←XΣ+1 and B+Π2←XΣ+1 transitions of the HC314N and HC315N isotopologues of cyanoacetylene have been recorded. The resolution of the photoelectron spectra allowed us to resolve the vibrational structures and the spin-orbit splittings in the cation. Accurate values of the adiabatic ionization potentials of the two isotopologues (EI/hc(HC314N)=93 909(2) cm-1 and EI/hc(HC315N)=93 912(2) cm-1), the vibrational frequencies of the ν2, ν6, and ν7 vibrational modes, and the spin-orbit coupling constant (ASO = -44(2) cm-1) of the X+Π2 cationic ground state have been derived from the measurements. Using ab initio calculations, the unexpected structure of the B+Π2←XΣ+1 transition is tentatively attributed to a conical intersection between the A+ and B+ electronic states of the cation.