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Calculated Aqueous Reduction Potentials of Neutral and Anionic Halogen Diatomic Molecules.
Andress, Thomas Dalton; Stanbury, David M; Dixon, David A.
Afiliación
  • Andress TD; Department of Chemistry and Biochemistry, The University of Alabama, Tuscaloosa, Alabama 35487, United States.
  • Stanbury DM; Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849, United States.
  • Dixon DA; Department of Chemistry and Biochemistry, The University of Alabama, Tuscaloosa, Alabama 35487, United States.
J Phys Chem A ; 128(31): 6494-6509, 2024 Aug 08.
Article en En | MEDLINE | ID: mdl-39082946
ABSTRACT
The free energy of hydration, aqueous, and gas phase electron affinity and aqueous reduction potentials of F2, Cl2, Br2, I2, ClF, BrF, IF, BrCl, ICl, IBr, and their corresponding anions were calculated using an electronic structure approach previously developed for these properties for X• and XO•, where X is a halogen which yielded excellent results. The gas phase electron affinities were calculated at the Feller-Peterson-Dixon level based on complete basis set extrapolation of CCSD(T) results with additional corrections. The agreement with the available experimental data is excellent, and the calculations provide a complete set of reliable electron affinities for these diatomic halogens. The hybrid solvation approach uses single point implicit solvation calculations on gas phase optimized clusters with explicit solvent molecules. The gas phase energy calculations were performed using MP2 and CCSD(T)-F12b for tetramer clusters (four explicit waters) and MP2 for octamer clusters (eight explicit waters). The final redox potentials were obtained at the MP2/aug-cc-pVTZ (aT) with a self-consistent reaction field (SMD) level using the octamer clusters. The aqueous reduction potentials of the neutral diatomic halogens are predicted within 0.06 V of the experiment for diatomic neutrals. The same agreement of 0.06 V is predicted for the redox potential resulting from dissociation electron attachment of the diatomic halogen anions. The current work extends reduction potentials for multiple redox couples for which no experimental data is available, for example, those containing iodine and the interhalogen anions. F2•- is predicted to dissociate for its lowest energy structure in both the tetramer and octamer clusters to form solvated F-, HF, and OH•.

Texto completo: 1 Colección: 01-internacional Banco de datos: MEDLINE Idioma: En Revista: J Phys Chem A Asunto de la revista: QUIMICA Año: 2024 Tipo del documento: Article País de afiliación: Estados Unidos

Texto completo: 1 Colección: 01-internacional Banco de datos: MEDLINE Idioma: En Revista: J Phys Chem A Asunto de la revista: QUIMICA Año: 2024 Tipo del documento: Article País de afiliación: Estados Unidos