Origin band of the first photoionizing transition of hydrogen isocyanide

Bérenger Gans (1) , Gustavo A Garcia (2) , Séverine Boyé-Péronne (1) , Stephen T Pratt , Jean-Claude Guillemin (3) , Alfredo Aguado (4) , Octavio Roncero (5) , Jean-Christophe Loison (6)

1 ISMO - Institut des Sciences Moléculaires d'Orsay
2 SSOLEIL - Synchrotron SOLEIL
3 ISCR - Institut des Sciences Chimiques de Rennes
4 CSIC - Consejo Superior de Investigaciones Cientificas [España] = Spanish National Research Council [Spain]
5 CSIC - Centro de Investigaciones Biológicas
6 ISM - Institut des Sciences Moléculaires

The photoelectron spectrum of the X1Σ+ → X+2Σ+ ionizing transition of hydrogen isocyanide (HNC) is measured for the first time at a fixed photon energy (13 eV). The assignment of the spectrum is supported by wave-packet calculations simulating the photoionization transition spectrum and using ab initio calculations of the potential energy surfaces for the three lowest electronic states of the cation. The photoelectron spectrum allows the retrieval of the fundamental of the CN stretching mode of the cationic ground state ([small nu, Greek, tilde]3 = 2260 ± 80 cm-1) and the adiabatic ionization energy of hydrogen isocyanide IE(HNC) = 12.011 ± 0.010 eV, which is far below that of HCN (IE(HCN) = 13.607 eV). In light of this latter result, the thermodynamics of the HCN+/HNC+ isomers is discussed and a short summary of the values available in the literature is given.

Domaines: Chimie

Bérenger Gans, Gustavo A Garcia, Séverine Boyé-Péronne, Stephen T Pratt, Jean-Claude Guillemin, et al.. Origin band of the first photoionizing transition of hydrogen isocyanide. Physical Chemistry Chemical Physics, 2019, 21 (5), pp.2337-2344. ⟨10.1039/c8cp07737a⟩. ⟨hal-02072205⟩