We report the first nitrogen 1s Auger-Meitner electron spectrum from a liquid ammonia microjet at a temperature of ∼223 K (-50 °C) and compare it with the simultaneously measured spectrum for gas-phase ammonia. The spectra from both phases are interpreted with the assistance of high-level electronic structure and ab initio molecular dynamics calculations. In addition to the regular Auger-Meitner-electron features, we observe electron emission at kinetic energies of 374-388 eV, above the leading Auger-Meitner peak (3a1 2). Based on the electronic structure calculations, we assign this peak to a shake-up satellite in the gas phase, i.e., Auger-Meitner emission from an intermediate state with additional valence excitation present. The high-energy contribution is significantly enhanced in the liquid phase. We consider various mechanisms contributing to this feature. First, in analogy with other hydrogen-bonded liquids (noticeably water), the high-energy signal may be a signature for an ultrafast proton transfer taking place before the electronic decay (proton transfer mediated charge separation). The ab initio dynamical calculations show, however, that such a process is much slower than electronic decay and is, thus, very unlikely. Next, we consider a non-local version of the Auger-Meitner decay, the Intermolecular Coulombic Decay. The electronic structure calculations support an important contribution of this purely electronic mechanism. Finally, we discuss a non-local enhancement of the shake-up processes.

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

Department of Physical Chemistry University of Chemistry and Technology Technická 5 Prague 6 16628 Czech Republic

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

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

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The well-known Auger-decay process was first discovered by Lise Meitner3 and then later rediscovered by Pierre Auger.4 We would like to give credit to this fact by following the naming suggestion of Ref. 5 and refer to the Auger–Meitner process throughout the paper.

See supplementary material at https://www.scitation.org/doi/suppl/10.1063/4.0000151 for a demonstration of the equivalency of the subtraction (method 1) and biasing (method 2) and for the procedure to prepare the satellite-free gas-phase spectrum shown in Fig. 2(b) and fitting procedure. We also provide computed energies of the initially N 1s core-ionized state, various intermediate and final states of the isolated ammonia molecule, the ammonia dimer, and the ammonia trimer. DOI

Observation of intermolecular Coulombic decay and shake-up satellites in liquid ammonia