• DOI:10.1039/c1cp20512a
• Corpus ID: 37388595

Assessment of an effective quasirelativistic methodology designed to study astatine chemistry in aqueous solution.

@article{Champion2011AssessmentOA,
  title={Assessment of an effective quasirelativistic methodology designed to study astatine chemistry in aqueous solution.},
  author={Julie Champion and Mahamadou Seydou and Andr{\'e}a Sabati{\'e}-Gogova and {\'E}ric Renault and Gilles Montavon and Nicolas Galland},
  journal={Physical chemistry chemical physics : PCCP},
  year={2011},
  volume={13 33},
  pages={
          14984-92
        }
}

• J. Champion, M. Seydou, +3 authors N. Galland
• Published 7 September 2011
• Chemistry
• Physical chemistry chemical physics : PCCP

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.