Calculation of Redox Potentials and pKa Values of Hydrated Transition Metal Cations by a Combined Density Functional and Continuum Dielectric Theory

Autor:	and Donald Bashford, Cindy L. Fisher, Jun L. Chen, Jian Li, Louis Noodleman
Rok vydání:	1996
Předmět:	Inorganic Chemistry Solvent Solvation shell Transition metal Continuum (measurement) Chemistry Inorganic chemistry Thermodynamics Density functional theory Dielectric Physical and Theoretical Chemistry Reaction field Redox
Zdroj:	Inorganic Chemistry. 35:4694-4702
ISSN:	1520-510X 0020-1669
DOI:	10.1021/ic951428f
Popis:	Density functional and continuum dielectric theories have been combined to calculate molecular properties such as hydration enthalpies, redox potentials, and absolute pKa values of transition metal cations in solution. The discrete cluster model, which is treated explicitly by density functional theory, includes six waters in the first hydration shell and another twelve waters in the second shell. The solvent reaction field is obtained from a finite-difference solution to the Poisson−Boltzmann equation and is coupled to the nonlocal density functional calculation in a self-consistent way. The calculated hydration enthalpies are 409, 1073, 431, and 1046 kcal/mol for Mn2+, Mn3+, Fe2+, and Fe3+, respectively, comparing fairly well to the experimental measurements of 440, 1087, 465, and 1060 kcal/mol. The calculated redox potentials for the Mn2+/Mn3+ and Fe2+/Fe3+ pairs are 1.59 and 1.06 V, respectively, in good agreement with the experimental values of 1.56 and 0.77 V. The computed absolute pKa values, 14.0,...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::3307346ddfc2a43b2dabf558a71c5510 https://doi.org/10.1021/ic951428f Zobrazit plný text záznamu