An experimental and theoretical study of the HNCO + ion

Abstract

The dissociations of energy-selected HNCO + ions have been examined at ionisation energies up to 40 eV using photoelectron–photoion coincidence spectroscopy. The slow metastable dissociation to HCO + is shown to occur from initial population of low vibrational levels within the doublet states corresponding to the third photoelectron band. Rate constants for the dissociation from several levels have been measured and the existence of an optical emission is predicted. High level calculations identify the third band in the photoelectron spectrum as an overlay of almost degenerate states arising from ionisation of the in-plane and out-of-plane bonding π-orbitals. The calculations suggest that at energies between 15.5 and 16 eV, the dominant pathway for dissociation involves slow internal conversion to the ground doublet state without surface crossing, followed by intersystem crossing to the quartet surface. At energies over 16 eV, two mechanisms are possible; intersystem crossing from the second excited doublet state to the lowest quartet surface in a cis-bent configuration, or internal conversion to the first excited doublet state via a surface crossing in the same region, followed by a second nonradiative transition to the doublet ground state and intersystem crossing to the quartet surface. In each case, the initial step is expected to be slow, consistent with the existence of an optical emission, and H-atom transfer occurs on the quartet surface via a ‘loose’ transition state leading to the direct formation of HCO + and N( 4S u).