Single-site N1s and O1s double core ionisation of the NO and N2O molecules has been studied using a magnetic bottle many-electron coincidence time-of-flight spectrometer at photon energies of 1100 eV and 1300 eV. The double core hole energies obtained for NO are 904.8 eV (N1s-2) and 1179.4 eV (O1s-2). The corresponding energies obtained for N 2O are 896.9 eV (terminal N1s-2), 906.5 eV (central N1s-2), and 1174.1 eV (O1s-2). The ratio between the double and single ionisation energies are in all cases close or equal to 2.20. Large chemical shifts are observed in some cases which suggest that reorganisation of the electrons upon the double ionization is significant. Δ-self-consistent field and complete active space self-consistent field (CASSCF) calculations were performed for both molecules and they are in good agreement with these results. Auger spectra of N2O, associated with the decay of the terminal and central N1s-2 as well as with the O1s-2 dicationic states, were extracted showing the two electrons emitted as a result of filling the double core holes. The spectra, which are interpreted using CASSCF and complete active space configuration interaction calculations, show atomic-like character. The cross section ratio between double and single core hole creation was estimated as 1.6 × 10-3 for nitrogen at 1100 eV and as 1.3 × 10-3 for oxygen at 1300 eV.
|Journal||Journal of Chemical Physics|
|Publication status||Published - 2014 Jan 28|
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry