Editor's ChoiceTracing electron solvation in Li−(NH3)n clusters with K-shell photodetachment spectroscopy

- K-shell photodetachment spectra of the bare Li− and Li−(NH3)n clusters are computed.
- Core level spectra are sensitive to ion-pairing.
- Numerous charge transfer satellites are found in the spectra of small clusters.
- Excitations of solvated electrons are seen in core level spectra.
- Three-electron processes play an important role in K-shell photodetachment of Li−.

We demonstrate that K-shell photoelectron spectroscopy is sensitive to binding motifs of cationic cores with excess electrons in solvated metals. Hereby, the satellites in core-level spectra and not the main line provide the important insight into ion-pairing effects. We found that contact ion-pairs in Li−(NH3)1-3 and a solvent-separated ion-pair in Li−(NH3)4 result in remarkably different Li1s spectra. The former spectra have numerous intense satellites of a charge-transfer character while that of Li−(NH3)4 contains only one strong satellite describing excitation of a solvated electron. We also explored K-shell photodetachment of the bare Li− and found that three-electron processes are essential here.

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