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Article: Ab initio quantum mechanical/molecular mechanical simulation of electron transfer process: Fractional electron approach
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TitleAb initio quantum mechanical/molecular mechanical simulation of electron transfer process: Fractional electron approach
 
AuthorsZeng, X1
Hu, H1
Hu, X1
Cohen, AJ1
Yang, W1
 
Issue Date2008
 
PublisherAmerican Institute of Physics. The Journal's web site is located at http://jcp.aip.org/jcp/staff.jsp
 
CitationJournal Of Chemical Physics, 2008, v. 128 n. 12 [How to Cite?]
DOI: http://dx.doi.org/10.1063/1.2832946
 
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.
 
ISSN0021-9606
2013 Impact Factor: 3.122
 
DOIhttp://dx.doi.org/10.1063/1.2832946
 
ReferencesReferences in Scopus
 
DC FieldValue
dc.contributor.authorZeng, X
 
dc.contributor.authorHu, H
 
dc.contributor.authorHu, X
 
dc.contributor.authorCohen, AJ
 
dc.contributor.authorYang, W
 
dc.date.accessioned2012-10-08T03:17:07Z
 
dc.date.available2012-10-08T03:17:07Z
 
dc.date.issued2008
 
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.
 
dc.description.naturelink_to_subscribed_fulltext
 
dc.identifier.citationJournal Of Chemical Physics, 2008, v. 128 n. 12 [How to Cite?]
DOI: http://dx.doi.org/10.1063/1.2832946
 
dc.identifier.doihttp://dx.doi.org/10.1063/1.2832946
 
dc.identifier.issn0021-9606
2013 Impact Factor: 3.122
 
dc.identifier.issue12
 
dc.identifier.pmid18376946
 
dc.identifier.scopuseid_2-s2.0-41549112442
 
dc.identifier.urihttp://hdl.handle.net/10722/168290
 
dc.identifier.volume128
 
dc.languageeng
 
dc.publisherAmerican Institute of Physics. The Journal's web site is located at http://jcp.aip.org/jcp/staff.jsp
 
dc.publisher.placeUnited States
 
dc.relation.ispartofJournal of Chemical Physics
 
dc.relation.referencesReferences in Scopus
 
dc.subject.meshComputer Simulation
 
dc.subject.meshElectrons
 
dc.subject.meshFerric Compounds - Chemistry
 
dc.subject.meshFerrous Compounds - Chemistry
 
dc.subject.meshModels, Chemical
 
dc.subject.meshOxidation-Reduction
 
dc.subject.meshQuantum Theory
 
dc.subject.meshRuthenium - Chemistry
 
dc.subject.meshWater - Chemistry
 
dc.titleAb initio quantum mechanical/molecular mechanical simulation of electron transfer process: Fractional electron approach
 
dc.typeArticle
 
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<contributor.author>Cohen, AJ</contributor.author>
<contributor.author>Yang, W</contributor.author>
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<description.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. &#169; 2008 American Institute of Physics.</description.abstract>
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Author Affiliations
  1. Duke University