Tx. Carroll et al., DEEXCITATION ELECTRON-SPECTROSCOPY OF CORE-EXCITED NO AS A FUNCTION OF EXCITATION-ENERGY, The Journal of chemical physics, 101(2), 1994, pp. 998-1005
Deexcitation electron spectra of core-excited NO have been measured at
several excitation energies in the N 1s --> 2 pi and O 1s --> 2 pi re
sonances. The nitrogen spectra exhibit significant variation with exci
tation energy; the, oxygen spectra vary only slightly. Sensitivity to
excitation energy occurs because each resonance represents the overlap
of three transitions to (2) Sigma(+), (2) Delta, and (2) Sigma(-) sta
tes, and each of these excited states decays to a unique set of levels
in the final-state ion. We have analyzed all spectra by taking into a
ccount excitation energy, lifetime-vibrational interference, and the o
rdering and splitting of the core-excited levels. Good agreement betwe
en calculated line shapes and experiment occurs if it assumed that the
level ordering is (2) Delta, (2) Sigma(-), (2) Sigma(+) for core-exci
ted nitrogen and (2) Sigma(-), (2) Delta, (2) Sigma(+) for core-excite
d oxygen. Photoexcitation data for oxygen have been analyzed to determ
ine the energies of these states 531.7, 532.7, and 533.7 eV. The deexc
itation spectrum from the (2) Delta State of nitrogen core-excited NO
to the ground state of NO+ has been analyzed using the theory of lifet
ime-vibrational interference to give a lifetime width for the core-exc
ited state of 146 meV. A similar analysis for the deexcitation of the
oxygen core-excited state is less conclusive, but is consistent with a
lifetime width of 180 meV.