Please use this identifier to cite or link to this item: http://dr.iiserpune.ac.in:8080/xmlui/handle/123456789/3266
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dc.contributor.authorKhungar, Bhartien_US
dc.contributor.authorRoy, Ankitaen_US
dc.contributor.authorKUMAR, ANANDen_US
dc.contributor.authorSadhu, Biswajiten_US
dc.contributor.authorSundararajan, Maheshen_US
dc.date.accessioned2019-07-01T05:35:12Z
dc.date.available2019-07-01T05:35:12Z
dc.date.issued2017-06en_US
dc.identifier.citationInternational Journal of Quantum Chemistry, 117(12), e25370.en_US
dc.identifier.issn0020-7608en_US
dc.identifier.issn1097-461Xen_US
dc.identifier.urihttp://dr.iiserpune.ac.in:8080/xmlui/handle/123456789/3266-
dc.identifier.urihttps://doi.org/10.1002/qua.25370en_US
dc.description.abstractA plethora of chemical reactions is redox driven processes. The conversion of toxic and highly soluble U(VI) complexes to nontoxic and insoluble U(IV) form are carried out through proton coupled electron transfer by iron containing cytochromes and mineral surfaces such as machinawite. This redox process takes place through the formation of U(V) species which is unstable and immediately undergo the disproportionation reaction. Thus, theoretical methods are extremely useful to understand the reduction process of U(VI) to U(V) species. We here have carried out the structures and reduction properties of several U(VI) to U(V) complexes using a variety of electronic structure methods. Due to the lack of experimental ionization energies for uranyl (UO2(V)‐UO2(VI)) couple, we have benchmarked the current and popularly used density functionals and cost effective ab initio methods against the experimental electron detachment energies of [UO2F4]1‐/2‐ and [UO2Cl4]1‐/2‐. We find that electron detachment energy of U(VI) predicted by RI‐MP2 level on the BP86 geometries correlate nicely with the experimental and CCSD(T) data. Based on our benchmark studies, we have predicted the structures and electron detachment energies of U(V) to U(VI) species for a series of uranium complexes at the RI‐MP2//BP86 level which are experimentally inaccessible till date. We find that the redox active molecular orbital is ligand centered for the oxidation of U(VI) species, where it is metal centered (primarily f‐orbital) for the oxidation of U(V) species. Finally, we have also calculated the detachment energies of a known uranyl [UO2]1+ complex whose X‐ray crystal structures of both oxidation states are available. The large bulky nature of the ligand stabilizing the uncommon U(V) species which cannot be routinely studied by present day CCSD(T) methods as the system size are more than 20–30 atoms. The success of our efficient computational strategy can be experimentally verified in the near future for the complex as the structures are stable in gas phase which can undergo oxidation.en_US
dc.language.isoenen_US
dc.publisherWileyen_US
dc.subjectPredicting the redox propertiesen_US
dc.subjectElectronic structure calculationsen_US
dc.subjectPlethora of chemical reactionsen_US
dc.subjectab initioen_US
dc.subjectDensity functional theoryen_US
dc.subjectRedox properties uranylen_US
dc.subject2017en_US
dc.titlePredicting the redox properties of uranyl complexes using electronic structure calculationsen_US
dc.typeArticleen_US
dc.contributor.departmentDept. of Chemistryen_US
dc.identifier.sourcetitleInternational Journal of Quantum Chemistryen_US
dc.publication.originofpublisherForeignen_US
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