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Journal of Chemical Physics / Volume 122 / Issue 23 / ARTICLES / Condensed Phase Dynamics, Structure, and Thermodynamics: Spectroscopy, Reactions, and Relaxation

J. Chem. Phys. 122, 234505 (2005); http://dx.doi.org/10.1063/1.1938192 (17 pages)

Density-functional molecular-dynamics study of the redox reactions of two anionic, aqueous transition-metal complexes

Yoshitaka Tateyama1, Jochen Blumberger2, Michiel Sprik2, and Ivano Tavernelli3

1Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom and National Institute for Material Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan
2Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom
3Institute of Molecular and Biological Chemistry, Swiss Federal Institute of Technology, Ecole Polytechnique Federal Lausanne (EPFL), Lausanne CH-1015, Switzerland

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(Received 15 March 2005; accepted 22 April 2005; published online 20 June 2005)

The thermochemistry of the RuO42−+MnO4−→RuO4−+MnO42− redox reaction in aqueous solution is studied by separate density-functional-based ab initio molecular-dynamics simulations of the component half reactions RuO42−→RuO4−+e− and MnO42−→MnO4−+e−. We compare the results of a recently developed grand-canonical method for the computation of oxidation free energies to the predictions by the energy-gap relations of the Marcus theory that can be assumed to apply to these reactions. The calculated redox potentials are in good agreement. The subtraction of the half-reaction free energies gives an estimate of the free energy of the full reaction. The result obtained from the grand-canonical method is −0.4 eV, while the application of the Marcus theory gives −0.3 eV. These should be compared to the experimental value of 0.0 eV. Size effects, in response to increasing the number of water molecules in the periodic model system from 30 to 48, are found to be small ( ≈ 0.1 eV). The link to the Marcus theory also has enabled us to compute reorganization free energies for oxidation. For both the MnO42− and RuO42− redox reactions we find the same reorganization free energy of 0.8 eV (1.0 eV in the larger system). The results for the free energies and further analysis of solvation and electronic structure confirm that these two tetrahedral oxoanions show very similar behavior in solution in spite of the central transition-metal atoms occupying a different row and column in the periodic table.

© 2005 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. THEORY AND COMPUTATIONAL METHODS
    1. Grand-canonical formalism
    2. Two-state model and numerical titration method
    3. Link to Marcus’s theory and histogram method
    4. Energy and entropy
    5. Technical details
  3. STRUCTURE AND ELECTRONIC STATES
    1. Solvation and molecular geometry
    2. Electronic states
  4. REACTION FREE ENERGIES
    1. Grand-canonical CPMD simulations
    2. Energetics: Franck–Condon cycle
    3. Reaction free energy according to Gaussian model
  5. DISCUSSION
    1. Similarity between MnO4 and RuO4
    2. Harmonic analysis of PES
    3. Finite-size effects
  6. CONCLUSION

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KEYWORDS and PACS

Keywords

ruthenium compounds, manganese compounds, reduction (chemical), negative ions, molecule-molecule reactions, ion-molecule reactions, oxidation, density functional theory, molecular dynamics method, ab initio calculations, free energy, reaction kinetics theory, thermochemistry

PACS

  • 82.30.Fi

    Ion-molecule, ion-ion, and charge-transfer reactions

  • 82.30.Cf

    Atom and radical reactions; chain reactions; molecule-molecule reactions

  • 82.60.Lf

    Thermodynamics of solutions

  • 82.20.Wt

    Computational modeling; simulation

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.1938192

PUBLICATION DATA

ISSN

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

Publisher

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

For access to fully linked references, you need to log in.
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