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Related Concept Videos

Ladder Diagrams: Redox Equilibria01:30

Ladder Diagrams: Redox Equilibria

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Ladder diagrams are useful tools for understanding redox equilibrium reactions, especially the effects of concentration changes on the electrochemical potential of the reaction. The vertical axis in the redox ladder diagrams represents the electrochemical potential, E. The area of predominance is demarcated using the Nernst equation.
Consider the Fe3+/Fe2+ half-reaction, which has a standard-state potential of +0.771 V. At potentials more positive than +0.771 V, Fe3+ predominates, whereas Fe2+...
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Redox Equilibria: Overview01:23

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A reduction-oxidation reaction is commonly called a redox reaction. In a redox reaction, electrons are transferred from one species to another rather than being shared between or among atoms. The reducing agent or reductant is the species that loses electrons and gets oxidized in the process. The species that gains electrons and gets reduced in the process is the oxidizing agent or oxidant. Redox reactions are represented as two separate equations called half-reactions, where one equation...
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The relative strength of an acid or base is the extent to which it ionizes when dissolved in water. If the ionization reaction is essentially complete, the acid or base is termed strong; if relatively little ionization occurs, the acid or base is weak. There are many more weak acids and bases than strong ones. The most common strong acids and bases are listed below:
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Weak Acid Solutions04:02

Weak Acid Solutions

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Few compounds act as strong acids. A far greater number of compounds behave as weak acids and only partially react with water, leaving a large majority of dissolved molecules in their original form and generating a relatively small amount of hydronium ions. Weak acids are commonly encountered in nature, being the substances partly responsible for the tangy taste of citrus fruits, the stinging sensation of insect bites, and the unpleasant smells associated with body odor. A familiar example of a...
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Standard Electrode Potentials03:02

Standard Electrode Potentials

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On comparing the reactivity of silver and lead, it is observed that the two ionic species, Ag+ (aq) and Pb2+ (aq), show a difference in their redox reactivity towards copper: the silver ion undergoes spontaneous reduction, while the lead ion does not. This relative redox activity can be easily quantified in electrochemical cells by a property called cell potential. This property is commonly known as cell voltage in electrochemistry, and it is a measure of the energy which accompanies the charge...
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The electrode interacts with ions in the electrolyte solution at its interface. The rate of oxidation and reduction depends on the speed at which electrons can transfer through this interface. As ions attach to or leave the electrode surface, the electrode acquires a charge, and an electrical potential forms across the interface, making the process more difficult to reach equilibrium. The charge on the electrode affects the local ion concentrations in the solution, though thermal motion...
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Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid
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Redox potentials and acidity constants from density functional theory based molecular dynamics.

Jun Cheng1, Xiandong Liu, Joost VandeVondele

  • 1Department of Chemistry, University of Aberdeen , Aberdeen AB24 3UE, United Kingdom.

Accounts of Chemical Research
|November 4, 2014
PubMed
Summary
This summary is machine-generated.

This study presents an all-atom computational method combining density functional theory molecular dynamics (DFTMD) and free energy perturbation (FEP) to accurately predict acidity constants (pKa) and redox potentials. The method achieves high accuracy for pKa and improved accuracy for redox potentials.

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Determination of the Gas-phase Acidities of Oligopeptides
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Area of Science:

  • Computational Chemistry
  • Physical Chemistry
  • Theoretical Chemistry

Background:

  • Accurate all-atom computation of acidity constants (pKa) and redox potentials remains a significant challenge.
  • Existing methods struggle to treat solute and solvent at the same level of electronic structure theory and statistical mechanics.
  • There is a need for robust computational tools to predict these fundamental chemical properties.

Purpose of the Study:

  • To review and present a combined density functional theory based molecular dynamics (DFTMD) and free energy perturbation (FEP) method for calculating pKa and redox potentials.
  • To demonstrate the capability of this method as a computational hydrogen electrode for accurate predictions.
  • To analyze the sources of error in computational predictions of pKa and redox potentials.

Main Methods:

  • Utilized a free energy perturbation (FEP) based method for reversible proton or electron insertion/removal in a periodic DFTMD model system.
  • Employed thermodynamic integration of vertical energy gaps to compute the free energy of insertion (work function).
  • Addressed the issue of physical reference loss in periodic boundary conditions by comparing with a proton work function.

Main Results:

  • pKa estimates computed using the proton insertion/removal scheme showed significantly higher accuracy than redox potential calculations.
  • The method, acting as a computational hydrogen electrode, allows direct comparison of DFTMD redox energies with experimental values.
  • Error analysis traced redox potential inaccuracies to the underestimation of the solvent's extended states energy gap, with hybrid functionals showing improvement.

Conclusions:

  • The presented DFTMD-FEP method provides accurate acidity constant predictions (1-2 pKa units uncertainty) when using hybrid functionals.
  • Redox potential calculations using this method achieve an error of approximately 0.2 V, with hybrid functionals offering improvements.
  • The study successfully separates DFT errors from finite system size and sampling uncertainties, offering insights into computational chemical predictions.