Open AccessOrigin band of the first photoionizing transition of hydrogen isocyanide
Author(s) -
Bérenger Gans,
Gustavo A. Garcia,
Séverine Boyé-Péronne,
S. T. Pratt,
JeanClaude Guillemin,
Alfredo Aguado,
Octavio Roncero,
JeanChristophe Loison
Publication year - 2019
Publication title -
physical chemistry chemical physics/pccp. physical chemistry chemical physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.053
H-Index - 239
eISSN - 1463-9084
pISSN - 1463-9076
DOI - 10.1039/c8cp07737a
Subject(s) - photoionization , chemistry , ionization energy , isocyanide , atomic physics , ionization , ab initio , photoemission spectroscopy , hydrogen , molecular electronic transition , ground state , ab initio quantum chemistry methods , photon energy , x ray photoelectron spectroscopy , ion , excited state , physics , photon , nuclear magnetic resonance , molecule , stereochemistry , organic chemistry , quantum mechanics
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.