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Journal of Chemical Physics / Volume 131 / Issue 15 / ARTICLES / Condensed Phase Dynamics, Structure, and Thermodynamics: Spectroscopy, Reactions, and Relaxation

J. Chem. Phys. 131, 154504 (2009); http://dx.doi.org/10.1063/1.3250438 (20 pages)

Redox potentials and pKa for benzoquinone from density functional theory based molecular dynamics

Jun Cheng, Marialore Sulpizi, and Michiel Sprik

Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom

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(Received 7 July 2009; accepted 24 September 2009; published online 19 October 2009)

The density functional theory based molecular dynamics (DFTMD) method for the computation of redox free energies presented in previous publications and the more recent modification for computation of acidity constants are reviewed. The method uses a half reaction scheme based on reversible insertion/removal of electrons and protons. The proton insertion is assisted by restraining potentials acting as chaperones. The procedure for relating the calculated deprotonation free energies to Brønsted acidities (pKa) and the oxidation free energies to electrode potentials with respect to the normal hydrogen electrode is discussed in some detail. The method is validated in an application to the reduction of aqueous 1,4-benzoquinone. The conversion of hydroquinone to quinone can take place via a number of alternative pathways consisting of combinations of acid dissociations, oxidations, or dehydrogenations. The free energy changes of all elementary steps (ten in total) are computed. The accuracy of the calculations is assessed by comparing the energies of different pathways for the same reaction (Hess’s law) and by comparison to experiment. This two-sided test enables us to separate the errors related with the restrictions on length and time scales accessible to DFTMD from the errors introduced by the DFT approximation. It is found that the DFT approximation is the main source of error for oxidation free energies.

© 2009 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. METHODS
    1. Free energies for half reactions from vertical energy gaps
    2. Restraining potentials and chemical species definition
    3. Finite system size and periodic boundary effects
    4. pKa and redox potentials from half reaction energies
    5. Corrections for restraints and zero point motion
    6. Computational setup
  3. RESULTS AND DISCUSSION
    1. Vertical energy gaps and free energy changes
    2. Solvent reorganization and hydration structure
    3. Comparison to experiment
    4. Summary of error analysis and evaluation of DFT
  4. CONCLUSION AND OUTLOOK

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KEYWORDS and PACS

Keywords

association, density functional theory, dissociation, electrodes, molecular dynamics method, organic compounds, oxidation, reaction kinetics theory, reduction (chemical)

PACS

  • 82.30.Nr

    Association, addition, insertion, cluster formation

  • 82.30.Lp

    Decomposition reactions (pyrolysis, dissociation, and fragmentation)

  • 82.20.Uv

    Stochastic theories of rate constants

  • 82.20.Db

    Transition state theory and statistical theories of rate constants

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3250438

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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