Core excitation, decay, and fragmentation in solid benzene as studied by x-ray absorption, resonant Auger, and photon stimulated desorption

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Abstract
For condensed benzene ice layers, core photoabsorption near edge structure (x‐ray absorption; recorded by Auger electron yield measurements), decay electron spectra for resonant and nonresonant excitation, and fragmentation as evident in yields of hydrogen and other ions, have been measured in the C1s region. The absorption spectrum is better resolved than most previously published spectra, exhibits some new features, and shows a high degree of parallelity to the spectrum of isolated molecules. Interestingly, the hydrogen ion yield indicates a particular dissociativeness of a certain core excitation resonance, X, which in the molecule has previously been assigned to a Rydberg state. This selective dissociation suggests that the responsible excitation is strongly antibonding for the carbon–hydrogen bond, while the degenerate Rydberg states broaden into a conduction band in the solid; and that the bond breaking probably occurs or at least starts in the core‐excited state, thus proceeding on an extremely short time scale, similarly to observations for other hydrogen‐containing molecules. The decay spectra are analyzed in terms of autoionization vs normal Auger decay and indicate that, apart from the first strong π resonance (which leads to pure autoionization) and the X resonance, the core resonances partly or fully ionize before core decay takes place. For the X resonance, the decay spectrum contains a contribution which cannot be assigned to intact benzene; this is taken as additional evidence for ultrafast dissociation, i.e., competitive with core decay. We use these results for a discussion of the influence of condensation on excitation, decay, and fragmentation.