Experimental S 2p-photoion yields of free SF6 (a) and clustered SF6 (b). The inset shows the redshift of the S 2p → 4eg-band of cluster (Clu.) relative to the molecular transition (Mol.) by 105 ± 5 meV (see text for further details).
The de-convoluted spin-orbit splitting of the S 2p 3/2,1/2 → 2t2g-transitions in molecular SF6 (a) and SF6-clusters (b). Experimental data are shown as dots. Solid lines represent results of fit functions containing contributions from asymmetric Lorentzians (cf. Eq. (7) ).
Spectral de-convolution of the S 2p 1/2,3/2 → 4eg-transition in molecular SF6 (a) and SF6-clusters (b). Experimental data are shown as dots. Solid lines represent results of fit functions containing contributions from asymmetric Lorentzians (cf. Eq. (7) ).
Spectral parameters of the individual spin-orbit split S 2p 3/2,1/2 components of the shape resonances in free and clustered SF6 extracted from the experimental data analysis. Energy positions derived from the experimental results (E max), maxima of the spectral distribution (E 0), Lorentzian and Gaussian FWHM ( ) and (W G), Lorentzian FWHM referring to 2p-hole decay and the photoelectron trapping time within the molecular cage are and , respectively. A convolution of a symmetric and asymmetric Lorentzian distribution is used in order to approximate the width . The superscript and the subscript Γ refer to t2g and eg denoting the shape resonances under study and the line asymmetry is denoted by α Γ. The error of the energy positions and the line asymmetry is estimated be ±5 meV and ±0.1 eV−1, respectively; the error of the widths and for 2t2g- and 4eg-shape resonances is estimated be ±10 meV and ±150 meV, respectively. See text for further details.
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