Calculated One-Electron Reduction Potentials and Solvation Structures for Selected p-Benzoquinones in Water

Autor:	Ralph A. Wheeler, and Anthony K. Grafton, Kevin S. Raymond
Rok vydání:	1997
Předmět:	Aqueous solution Chemistry Solvation Thermodynamics Electrochemistry Redox Surfaces Coatings and Films Free energy perturbation Molecular dynamics Materials Chemistry One-electron reduction Molecule Physical and Theoretical Chemistry Atomic physics
Zdroj:	The Journal of Physical Chemistry B. 101:623-631
ISSN:	1520-5207 1520-6106
DOI:	10.1021/jp961852h
Popis:	The one-electron reduction of quinones is important not only in electrochemistry but also in biochemical energy storage, energy utilization, and organic chemcial reactions. Thermodynamic cycles are investigated to estimate aqueous one-electron reduction potentials for the redox indicators p-benzoquinone and p-duroquinone, as well as chloro-substituted p-benzoquinones. Gas-phase reduction free energy differences are approximated from electron affinities calculated by using the hybrid Hartree−Fock/density-functional B3LYP method, a semiempirical quantum chemical method that expresses a molecule's exchange-correlation energy as a weighted sum of Hartree−Fock, local, and gradient-corrected density-functional energies. Free energy perturbation theory was used with molecular dynamics simulations (at constant temperature, pressure, and number of atoms) to estimate hydration free energy differences. Calculated one-electron reduction potentials for the quinones are within 10−190 meV of experimental values. An exce...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::104150410b5a0b209254df9be6dfcaa6 https://doi.org/10.1021/jp961852h Zobrazit plný text záznamu