We report valence band photoelectron spectroscopy measurements of gas-phase and liquid-phase benzene as well as those of benzene dissolved in liquid ammonia, complemented by electronic structure calculations. The origins of the sizable gas-to-liquid-phase shifts in electron binding energies deduced from the benzene valence band spectral features are quantitatively characterized in terms of the Born-Haber solvation model. This model also allows to rationalize the observation of almost identical shifts in liquid ammonia and benzene despite the fact that the former solvent is polar while the latter is not. For neutral solutes like benzene, it is the electronic polarization response determined by the high frequency dielectric constant of the solvent, which is practically the same in the two liquids, that primarily determines the observed gas-to-liquid shifts.

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

Helmholtz Zentrum Berlin für Materialien und Energie Hahn Meitner Platz 1 D 14109 Berlin Germany

Institut für Kernphysik Goethe Universität Frankfurt Max von Laue Str 1 D 60438 Frankfurt am Main Germany

Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Flemingovo nám 2 166 10 Prague 6 Czech Republic

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

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