Assessment of an effective quasirelativistic methodology designed to study astatine chemistry in aqueous solution
Literature Information
Andrea Sabatié-Gogova, Eric Renault, Gilles Montavon, Nicolas Galland
A cost-effective computational methodology designed to study astatine (At) chemistry in aqueous solution has been established. It is based on two-component spin–orbit density functional theory calculations and solvation calculations using the conductor-like polarizable continuum model in conjunction with specific astatine cavities. Theoretical calculations are confronted with experimental data measured for complexation reactions between metallic forms of astatine (At+ and AtO+) and inorganic ligands (Cl−, Br− and SCN−). For each reaction, both 1 ∶ 1 and 1 ∶ 2 complexes are evidenced. The experimental trends regarding the thermodynamic constants (K) can be reproduced qualitatively and quantitatively. The mean signed error on computed Log K values is −0.4, which corresponds to a mean signed error smaller than 1 kcal mol−1 on free energies of reaction. Theoretical investigations show that the reactivity of cationic species of astatine is highly sensitive to spin–orbit coupling and solvent effects. At the moment, the presented computational methodology appears to be the only tool to gain an insight into astatine chemistry at a molecular level.
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Physical Chemistry Chemical Physics

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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