Formation and localization of a solvated electron in ground and low-lying excited states of Li(NH3)n and Li(H2O)nclusters: a comparison with Na(NH3)n and Na(H2O)n

Literature Information

Publication Date 2009-08-25
DOI 10.1039/B907766A
Impact Factor 3.676
Authors

Kenro Hashimoto, Kota Daigoku


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Abstract

A theoretical study of the ground and low-lying excited states of Li(NH3)n and Li(H2O)n (n = 1–8) clusters is presented. Their structures, binding energies, vertical ionization energies and vertical transition energies were calculated using ab initio molecular orbital methods at correlated levels. Compared with Na(NH3)n and Na(H2O)n, the incremental binding energies and the spectroscopic energies are found to be almost metal-independent, but solvent-dependent after first-shell closure in both M(NH3)n and M(H2O)n (M = Li and Na) clusters. Autoionization of the alkali atoms occurs via a spatial expansion of unpaired electron distribution extending to outside of the first solvation-shell, irrespective of the combinations of the metal and the solvent. The localization mode of the wave function of the solvated electron was investigated in both the ground and excited states. A change from a one-center diffuse state to a two-center localized state proceeds more quickly against n in M(H2O)n than in M(NH3)n, which is behind the solvent-dependence of the evaluated quantities.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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