Description
Understanding ultrafast relaxation following inner-shell ionization is central to XUV/X-ray spectroscopy and attosecond science. Electron-transfer-mediated decay (ETMD) is an efficient nonlocal mechanism for charge and energy redistribution in weakly bound systems, triggered by core ionization. We investigate a loosely bound NeKr₂ trimer as a prototype system, combining theoretical modeling with recently reported five-fold coincidence measurements [1,2]. We assess the competition between ETMD, which drives Coulomb explosion, and direct dissociation without ETMD, and quantify ETMD efficiency in asymmetric configurations, where charge transfer occurs along the shorter Ne–Kr distance and energy transfer along the longer one. Depending on the decay time, specific classes of molecular geometries are favored, providing an intuitive picture of the decay mechanism and indicating a roaming-like nuclear motion prior to fragmentation. The results highlight the role of nuclear dynamics and geometry in ultrafast decay and provide a basis for understanding ETMD in more complex environments.
References:
[1] Hofierka et al., J. Chem. Theory Comput. 2025, 21, 12026–12033
[2] Trinter et al., J. Am. Chem. Soc. 2026, 148, 4126–4135
