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dc.contributor.authorLiu, Xiandongen
dc.contributor.authorCheng, Junen
dc.contributor.authorSprik, Michielen
dc.date.accessioned2015-01-12T14:22:40Z
dc.date.available2015-01-12T14:22:40Z
dc.date.issued2014-11-11en
dc.identifier.citationThe Journal of Physical Chemistry B 2015, 119 (3), pp 1152–1163. DOI: 10.1021/jp506691hen
dc.identifier.issn1520-6106
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/246563
dc.description.abstractThe 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.
dc.description.sponsorshipWe 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).
dc.languageEnglishen
dc.language.isoenen
dc.publisherAmerican Chemical Society
dc.subjectAqueous redox chemistry,en
dc.subjectcomputational chemistryen
dc.subjectdensity functional theoryen
dc.titleAqueous Transition Metal Cations as Impurities in a Wide Gap Oxide: The Cu^2+/Cu^1+ and Ag^2+/Ag^1+ Redox Couples Revisiteden
dc.typeArticle
dc.description.versionThis is the accepted manuscript. The final version is available from ACS at http://pubs.acs.org/doi/abs/10.1021/jp506691h.en
prism.endingPage1163
prism.publicationDate2014en
prism.publicationNameThe Journal of Physical Chemistry Ben
prism.startingPage1152
prism.volume119en
rioxxterms.versionofrecord10.1021/jp506691hen
rioxxterms.licenseref.urihttp://www.rioxx.net/licenses/all-rights-reserveden
rioxxterms.licenseref.startdate2014-11-11en
dc.contributor.orcidSprik, Michiel [0000-0001-7449-3408]
dc.identifier.eissn1520-5207
rioxxterms.typeJournal Article/Reviewen
rioxxterms.freetoread.startdate2015-11-11


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