Origin band of the first photoionizing transition of hydrogen isocyanide

Abstract

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 (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.