Experimental studies of the electronic structure of excess electrons in liquids-archetypal quantum solutes-have been largely restricted to very dilute electron concentrations. We overcame this limitation by applying soft x-ray photoelectron spectroscopy to characterize excess electrons originating from steadily increasing amounts of alkali metals dissolved in refrigerated liquid ammonia microjets. As concentration rises, a narrow peak at ~2 electron volts, corresponding to vertical photodetachment of localized solvated electrons and dielectrons, transforms continuously into a band with a sharp Fermi edge accompanied by a plasmon peak, characteristic of delocalized metallic electrons. Through our experimental approach combined with ab initio calculations of localized electrons and dielectrons, we obtain a clear picture of the energetics and density of states of the ammoniated electrons over the gradual transition from dilute blue electrolytes to concentrated bronze metallic solutions.

Charles University Faculty of Mathematics and Physics Ke Karlovu 3 121 16 Prague 2 Czech Republic

Département de Chimie École Normale Supérieure PSL University 75005 Paris France

Department of Chemistry Graduate School of Science Kyoto University Kitashirakawa Oiwakecho Sakyo Ku Kyoto 606 8502 Japan

Department of Chemistry Humboldt Universität zu Berlin Brook Taylor Str 2 D 12489 Berlin Germany

Department of Chemistry University of Southern California Los Angeles CA 90089 0482 USA

Helmholtz Zentrum Berlin für Materialien und Energie Albert Einstein Strasse 15 D 12489 Berlin Germany

Institute of Organic Chemistry and Biochemistry Czech Academy of Sciences Flemingovo nám 2 16610 Prague 6 Czech Republic

Molecular Physics Fritz Haber Institut der Max Planck Gesellschaft Faradayweg 4 6 D 14195 Berlin Germany

Science. 2020 Jun 5;368(6495):1056-1057. doi: 10.1126/science.abb9717. PubMed

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