Aqueous Transition Metal Cations as Impurities in a Wide Gap Oxide: The Cu^2+/Cu^1+ and Ag^2+/Ag^1+ Redox Couples Revisited
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Publication Date
2014-11-11Journal Title
The Journal of Physical Chemistry B
ISSN
1520-6106
Publisher
American Chemical Society
Volume
119
Pages
1152-1163
Language
English
Type
Article
Metadata
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Liu, X., Cheng, J., & Sprik, M. (2014). Aqueous Transition Metal Cations as Impurities in a Wide Gap Oxide: The Cu^2+/Cu^1+ and Ag^2+/Ag^1+ Redox Couples Revisited. The Journal of Physical Chemistry B, 119 1152-1163. https://doi.org/10.1021/jp506691h
Abstract
The interactions of the d electrons of transition metal aqua ions with the solvent are
usually divided in short range electronic interactions with ligand water molecules and
long range electrostatic interactions with molecules beyond the rst coordination shell.
This is the rationale behind the cluster continuum and QM/MM methods developed
for the computation of the redox potentials. In the density functional theory based
molecular dynamics (DFTMD) method the electronic states of the complex are also
allowed to mix with the extended band states of the solvent. Returning to the Cu1+ and
Ag1+ oxidation reaction which has been the subject of DFTMD simulation before we
show that coupling to the valence band states of water is greatly enhanced by the band
gap error in the density functional approximation commonly used in DFTMD (the
generalized gradient approximation). This e ect is analyzed by viewing the solvent
as a wide gap oxide and the redox active ions as electronic defects. The errors can
be reduced signi cantly by application of hybrid functionals containing a fraction of
Hartree-Fock exchange. These calculations make use of recent progress in DFTMD
technology enabling us to include sp core polarization and Hartree-Fock exchange in
condensed phase model systems.
Keywords
Aqueous redox chemistry,, computational chemistry, density functional theory
Sponsorship
We acknowledge
grants from the National Science Foundation of China (Nos. 41002013, 41222015 and
41273074) and Newton International Fellowship program. Further support came from the
State Key Laboratory for Mineral Deposits Research in Nanjing University and the Foundation
for the Author of National Excellent Doctoral Dissertation of PR China (No.201228).
Identifiers
External DOI: https://doi.org/10.1021/jp506691h
This record's URL: https://www.repository.cam.ac.uk/handle/1810/246563
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