Observing pre-edge K -shell resonances in Kr, Xe, and XeF 2

The $1s\phantom{\rule{4pt}{0ex}}\ensuremath{\rightarrow}\phantom{\rule{4pt}{0ex}}np$ Rydberg transitions below the $1s$ ionization thresholds of Kr and Xe are obscured in x-ray absorption spectra due to core-hole lifetime broadening. However, the $np$ spectator electrons associated with those resonances can affect the core-hole decay spectra. We report on ion charge-state distributions of Kr and Xe measured in coincidence with ${KL}_{2,3}$ ($K{\ensuremath{\alpha}}_{1,2}$), ${KM}_{2,3}$ ($K{\ensuremath{\beta}}_{1,3}$), and ${\mathrm{KN}}_{2,3}$ ($K{\ensuremath{\beta}}_{2}$) x-ray fluorescence as the incident x-ray energy is scanned through pre-edge resonances and ionization thresholds. The coincidence measurements select vacancy cascades that begin with a radiative transition that transfers $1s$ holes to the $2p$, $3p$, and $4p$ shells followed by emission of Auger electrons. We observe shifts of ion yields from higher to lower charge states that we attribute to $np$ spectator electrons. For the special case of ${\mathrm{Kr}}^{1+}$ that is produced in coincidence with $K{\ensuremath{\beta}}_{2}$ x rays, the ion yield decreases in the pre-edge region. This is attributed to production of neutral, metastable Kr $4{p}^{\ensuremath{-}1}np$ states that reduce the ${\mathrm{Kr}}^{1+}$ yield. Model fits to the x-ray absorption spectra are presented to show the lifetime broadened pre-edge resonances and ionization thresholds. High-level relativistic coupled-cluster calculations that treat relativistic, electron correlation, and wave function relaxation effects on the same footing obtain agreement with the experimental $1s$ ionization energies of Kr and Xe to $l2$ eV. The Xe $K$-edge x-ray absorption spectrum and ion charge-state distributions of ${\mathrm{XeF}}_{2}$ were also recorded. Excitation of the $7{\ensuremath{\sigma}}_{u}$ lowest unoccupied molecular orbital (LUMO) in ${\mathrm{XeF}}_{2}$ is observed in the pre-edge region. Our ab initio calculations find that the $6{p}_{z}$ Rydberg state is strongly perturbed by the presence of the $7{\ensuremath{\sigma}}_{u}$ LUMO. A fit to the measured LUMO, $6{p}_{x}$, $6{p}_{y}$, $6{p}_{z}$ Rydberg states, and ionization threshold is guided by the relativistic coupled-cluster calculations. The F ligands modify the valence electron charge distribution and result in a $\ensuremath{\sim}2.3$ eV chemical shift of the Xe $1s$ ionization energy relative to atomic Xe. Xe $1{s}^{\ensuremath{-}1}$ core-hole decay in ${\mathrm{XeF}}_{2}$ results in ionization of the F ligands and energetic fragmentation into atomic ions. Ion charge-state spectra of ${\mathrm{XeF}}_{2}$ were recorded in coincidence with x-ray fluorescence for excitation on the LUMO resonance and above the Xe $1s$ ionization threshold. For the ion time of flight spectra recorded on the LUMO resonance, the ${\mathrm{F}}^{q+}$ ($q=1$--4) peaks are split into two peaks along the linear polarization direction of the incident x-ray beam. This effect is attributed to spatial alignment of ${\mathrm{XeF}}_{2}$ molecules by resonant x-ray absorption, and the peak splittings are used to measure the F ion fragmentation energies following $K{\ensuremath{\alpha}}_{1,2}$, $K{\ensuremath{\beta}}_{1,3}$, and $K{\ensuremath{\beta}}_{2}$ x-ray fluorescence. We observe variations of the F ion charge state yields and fragmentation energies for the three fluorescence pathways that leave the molecule in different outer-shell hole states.