Structure and fragmentation of doubly ionized HNCS

Abstract

Double ionization spectra of isothiocyanic acid (HNCS) have been measured using multi-electron and multi-ion coincidence techniques combined with high-level theoretical calculations. The adiabatic double ionization energy of HNCS is found at 27.1 ± 0.1 eV and is associated with the formation of the X 3A″ ground state of HNCS2+. The characteristics of different dissociation channels are examined and compared to the results of electronic structure calculations obtained by systematically elongating the three bonds H–NCS, HN–CS, and HNC–S. For instance, the adiabatic double ionization energy of the NCS fragment is deduced to be 30.95 ± 0.5 eV. In addition, the C+ and NS+ dissociation channels are of particular interest, possibly indicating the involvement of a structural rearrangement process upon doubly ionizing HNCS.