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Article: Ab initio quantum mechanical/molecular mechanical simulation of electron transfer process: Fractional electron approach

TitleAb initio quantum mechanical/molecular mechanical simulation of electron transfer process: Fractional electron approach
Authors
Issue Date2008
PublisherAmerican Institute of Physics. The Journal's web site is located at http://jcp.aip.org/jcp/staff.jsp
Citation
Journal Of Chemical Physics, 2008, v. 128 n. 12 How to Cite?
Abstract
Electron transfer (ET) reactions are one of the most important processes in chemistry and biology. Because of the quantum nature of the processes and the complicated roles of the solvent, theoretical study of ET processes is challenging. To simulate ET processes at the electronic level, we have developed an efficient density functional theory (DFT) quantum mechanical (QM)/molecular mechanical (MM) approach that uses the fractional number of electrons as the order parameter to calculate the redox free energy of ET reactions in solution. We applied this method to study the ET reactions of the aqueous metal complexes Fe (H2 O) 6 2+/3+ and Ru (H2 O) 6 2+/3+. The calculated oxidation potentials, 5.82 eV for Fe(II/III) and 5.14 eV for Ru(II/III), agree well with the experimental data, 5.50 and 4.96 eV, for iron and ruthenium, respectively. Furthermore, we have constructed the diabatic free energy surfaces from histogram analysis based on the molecular dynamics trajectories. The resulting reorganization energy and the diabatic activation energy also show good agreement with experimental data. Our calculations show that using the fractional number of electrons (FNE) as the order parameter in the thermodynamic integration process leads to efficient sampling and validate the ab initio QM/MM approach in the calculation of redox free energies. © 2008 American Institute of Physics.
Persistent Identifierhttp://hdl.handle.net/10722/168290
ISSN
2013 Impact Factor: 3.122
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorZeng, Xen_US
dc.contributor.authorHu, Hen_US
dc.contributor.authorHu, Xen_US
dc.contributor.authorCohen, AJen_US
dc.contributor.authorYang, Wen_US
dc.date.accessioned2012-10-08T03:17:07Z-
dc.date.available2012-10-08T03:17:07Z-
dc.date.issued2008en_US
dc.identifier.citationJournal Of Chemical Physics, 2008, v. 128 n. 12en_US
dc.identifier.issn0021-9606en_US
dc.identifier.urihttp://hdl.handle.net/10722/168290-
dc.description.abstractElectron transfer (ET) reactions are one of the most important processes in chemistry and biology. Because of the quantum nature of the processes and the complicated roles of the solvent, theoretical study of ET processes is challenging. To simulate ET processes at the electronic level, we have developed an efficient density functional theory (DFT) quantum mechanical (QM)/molecular mechanical (MM) approach that uses the fractional number of electrons as the order parameter to calculate the redox free energy of ET reactions in solution. We applied this method to study the ET reactions of the aqueous metal complexes Fe (H2 O) 6 2+/3+ and Ru (H2 O) 6 2+/3+. The calculated oxidation potentials, 5.82 eV for Fe(II/III) and 5.14 eV for Ru(II/III), agree well with the experimental data, 5.50 and 4.96 eV, for iron and ruthenium, respectively. Furthermore, we have constructed the diabatic free energy surfaces from histogram analysis based on the molecular dynamics trajectories. The resulting reorganization energy and the diabatic activation energy also show good agreement with experimental data. Our calculations show that using the fractional number of electrons (FNE) as the order parameter in the thermodynamic integration process leads to efficient sampling and validate the ab initio QM/MM approach in the calculation of redox free energies. © 2008 American Institute of Physics.en_US
dc.languageengen_US
dc.publisherAmerican Institute of Physics. The Journal's web site is located at http://jcp.aip.org/jcp/staff.jspen_US
dc.relation.ispartofJournal of Chemical Physicsen_US
dc.subject.meshComputer Simulationen_US
dc.subject.meshElectronsen_US
dc.subject.meshFerric Compounds - Chemistryen_US
dc.subject.meshFerrous Compounds - Chemistryen_US
dc.subject.meshModels, Chemicalen_US
dc.subject.meshOxidation-Reductionen_US
dc.subject.meshQuantum Theoryen_US
dc.subject.meshRuthenium - Chemistryen_US
dc.subject.meshWater - Chemistryen_US
dc.titleAb initio quantum mechanical/molecular mechanical simulation of electron transfer process: Fractional electron approachen_US
dc.typeArticleen_US
dc.identifier.emailHu, H:haohu@hku.hken_US
dc.identifier.authorityHu, H=rp00707en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1063/1.2832946en_US
dc.identifier.pmid18376946en_US
dc.identifier.scopuseid_2-s2.0-41549112442en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-41549112442&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume128en_US
dc.identifier.issue12en_US
dc.identifier.isiWOS:000254537200047-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridZeng, X=7403247770en_US
dc.identifier.scopusauthoridHu, H=7404097564en_US
dc.identifier.scopusauthoridHu, X=12782008400en_US
dc.identifier.scopusauthoridCohen, AJ=7404781388en_US
dc.identifier.scopusauthoridYang, W=7407757509en_US

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