Effect of charge and solvation shell on non-radiative decay processes in s-block cationic metal ion water clusters

Intermolecular Coulombic decay or electron transfer-mediated decay are the autoionization processes through which a molecule can relax. This relaxation is only possible if the inner valence's ionization potential (IP) exceeds the system's double ionization potential (DIP). To study the effects of charge and solvation shell, we have calculated the IP, DIP values, and lifetime of Na-2s and Mg-2s temporary bound states in various optimized structures of Na+-(H2O)(n) and Mg2+-(H2O)(n) (n = 1-5) micro-solvated clusters, where n water molecules are distributed in a way that some are directly bound to the metal ion and the rest to the water molecules. The first and second solvation shells are the names for the former and the latter water-binding positions, respectively. For a given n, the lifetime of decaying states is longer when water molecules are in the second solvation shell. We found that the Mg-2p state can decay for all n values in Mg2+-(H2O)(n) clusters, whereas the Na-2p state's decay is possible for n >= 2 in Na+-(H2O)(n) clusters. Our findings highlight the influence of metal ions' charge, different solvation shell structures, and the number of water molecules on the decay rate. These systems are relevant to the human body, which makes this study significant.

Automated summary

Molecules can relax through intermolecular Coulombic decay or electron transfer-mediated decay processes. This study investigated the effects of charge and solvation shell on the relaxation process. Calculations were done on Na+-(H2O)(n) and Mg2+-(H2O)(n) micro-solvated clusters to determine the ionization potential, double ionization potential, and lifetime of Na-2s and Mg-2s temporary bound states. The findings highlight the influence of metal ions' charge, solvation shell structures, and the number of water molecules on the decay rate. The relevance of these systems to the human body adds significance to this study.