Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 14, Issue 6, Pages 1418-1426Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.2c03654
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After ionization, cation-radicals store internal energy. Auger decay may trigger electron ejection and molecule fragmentation, while intermolecular Coulombic decay and electron-transfer mediated decay prevent fragmentation. The relaxation processes of prototypical heterocycle-water complexes depend on the hydrogen-bonding site, which determines the nature and energetics of involved electronic states. The presence of electron-density donating or accepting neighbor influences the relaxation mechanisms of biologically relevant systems.
After ionization of an inner-valence electron of molecules, the resulting cation -radicals store substantial internal energy which, if sufficient, can trigger ejection of an additional electron in an Auger decay usually followed by molecule fragmentation. In the environment, intermolecular Coulombic decay (ICD) and electron-transfer mediated decay (ETMD) are also operative, resulting in one or two electrons being ejected from a neighbor, thus preventing the fragmentation of the initially ionized molecule. These relaxation processes are investigated theoretically for prototypical heterocycle-water complexes of imidazole, pyrrole, and pyridine. It is found that the hydrogen-bonding site of the water molecule critically influences the nature and energetics of the electronic states involved, opening or closing certain relaxation processes of the inner-valence ionized system. Our results indicate that the relaxation mechanisms of biologically relevant systems with inner-valence vacancies on their carbon atoms can strongly depend on the presence of the electron-density donating or accepting neighbor, either water or another biomolecule.
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