Schewe, H.C.; Muchová, E.; Belina, M.; Buttersack, T.; Stemer, D.; Seidel, R.; Thürmer, S.; Slavícek, P.; Winter, B.: Observation of intermolecular Coulombic decay and shake-up satellites in liquid ammonia. Structural Dynamics 9 (2022), p. 044901/1-12
10.1063/4.0000151
Open Access Version
Abstract:
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 (3a12). 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.