Two-Sided Impact of Water on the Relaxation of Inner-Valence Vacancies of Biologically Relevant Molecules

TL;DR

This study investigates how water molecules influence the relaxation processes of inner-valence vacancies in biologically relevant molecules, revealing that hydrogen-bonding sites critically affect electronic state dynamics and decay pathways.

Contribution

It provides a theoretical analysis of water's impact on relaxation mechanisms of inner-valence ionized molecules, highlighting the role of hydrogen-bonding sites in biological environments.

Findings

Hydrogen-bonding sites in water critically influence relaxation pathways.

Water presence can open or close specific decay processes.

Relaxation mechanisms depend on the electron-donating or accepting nature of neighboring molecules.

Abstract

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.