Prediction of Aqueous Reduction Potentials of X•, ChH•, and XO• Radicals with X = Halogen and Ch = Chalcogen

Andress, Thomas Dalton; Maxwell, Jackson W.; McNeill, Ashley S.; Stanbury, David M.; Dixon, David A.

doi:10.1021/acs.jpca.3c06123

Cited by 1 publication

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“…The geometries of the low energy conformers were found to be similar to those previously predicted when calculating the aqueous reduction potentials of hypohalites . Cluster 4 A consists of the four explicit waters practically unchanged from the lowest energy water tetramer with the interhalogen interacting with an explicit water’s lone pair through the halogen with the lower electronegativity.…”

Section: Resultssupporting

confidence: 67%

“…The initial geometries for the tetramers and the octamers were taken from our previous work on the aqueous reduction potential of halogen, hypohalite, or chalcogen containing radicals . The A , B , and C octamer geometries for all four dihalogens are similar to the hypohalite (halogen oxide) and chalcogen hydride radical-water cluster geometries found previously (Figure ).…”

Section: Resultsmentioning

confidence: 81%

“…Previous work involving the prediction of p K a values of halogen acids, oxy-halide acids, and chalcogen hydrides provided the anion hydration energies of the monatomic halogens needed to calculate the reduction potentials for the X 2 •– and XY •– species. Our group has previously predicted the aqueous reduction potentials of X • , ChH • , and XO • radicals where X = halogen and Ch = chalcogen that showed excellent agreement with experimental reduction potentials. Experimental redox values for Cl 2 , Br 2 , I 2 , Cl 2 •– , Br 2 •– , and I 2 •– are available from an IUPAC technical report and from an earlier compilation by Stanbury .…”

Section: Introductionmentioning

confidence: 64%

“…For the calculations with explicit water molecules included, the cluster geometries were optimized at the MP2/aD level for the tetramers and octamers with and without the halogen species present. The number of water molecules chosen for the cluster models is based on our prior work. ,, The vibrational frequencies of the water clusters with and without addition of a halogen were calculated at the MP2/aD level in the gas phase. Single point solvation calculations with optimized geometries were performed at the MP2/aT level using the self-consistent reaction field (SCRF) approach with the SMD model based on our previous work on the redox potentials of the halogen atoms .…”

Section: Methodsmentioning

confidence: 99%

“…The number of water molecules chosen for the cluster models is based on our prior work. ,, The vibrational frequencies of the water clusters with and without addition of a halogen were calculated at the MP2/aD level in the gas phase. Single point solvation calculations with optimized geometries were performed at the MP2/aT level using the self-consistent reaction field (SCRF) approach with the SMD model based on our previous work on the redox potentials of the halogen atoms . The SMD model includes additional nonelectrostatic terms.…”

Section: Methodsmentioning

confidence: 99%

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Calculated Aqueous Reduction Potentials of Neutral and Anionic Halogen Diatomic Molecules

Andress,

Stanbury,

Dixon

2024

J. Phys. Chem. A

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The free energy of hydration, aqueous, and gas phase electron affinity and aqueous reduction potentials of F 2 , Cl 2 , Br 2 , I 2 , 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. F 2•− is predicted to dissociate for its lowest energy structure in both the tetramer and octamer clusters to form solvated F − , HF, and OH • .

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Section: Resultssupporting

confidence: 67%

Section: Resultsmentioning

confidence: 81%