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Oxygen exchange in uranyl hydroxide via two "nonclassical" ions
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dc.contributor.author | Buehl, Michael | |
dc.contributor.author | Schreckenbach, Georg | |
dc.date.accessioned | 2011-03-31T15:01:02Z | |
dc.date.available | 2011-03-31T15:01:02Z | |
dc.date.issued | 2010-04-19 | |
dc.identifier.citation | Buehl , M & Schreckenbach , G 2010 , ' Oxygen exchange in uranyl hydroxide via two "nonclassical" ions ' , Inorganic Chemistry , vol. 49 , no. 8 , pp. 3821-3827 . https://doi.org/10.1021/ic902508z | en |
dc.identifier.issn | 0020-1669 | |
dc.identifier.other | PURE: 5310792 | |
dc.identifier.other | PURE UUID: 7ebc67e1-ebab-493e-ac0a-f99b177b1300 | |
dc.identifier.other | WOS: 000276556900037 | |
dc.identifier.other | Scopus: 77951010931 | |
dc.identifier.other | ORCID: /0000-0002-1095-7143/work/48131769 | |
dc.identifier.uri | https://hdl.handle.net/10023/1751 | |
dc.description.abstract | A recently proposed pathway for the scrambling of axial (uranyl) and equatorial 0 atoms in [UO2(OH)4]2- (1) is refined using Car-Parrinello molecular dynamics (CPMD) simulations in an explicit solvent (water) and with model counterions (NH4+). According to constrained CPMD/BLYP simulations and thermodynamic integration, 1 can be deprotonated to [UO3(OH)3]3- with a T-shaped UO3 group (Delta A = 7.1 kcal/mol), which in turn can undergo a solvent-assisted proton transfer via a cis-[UO2(OH)4]2-center dot OH- complex and a total overall barrier of Delta A(double dagger) = 12.5 kcal/mol. According to computed relative energies of trans- and cis-[UO2(OH)4]2- in the gas phase and in a polarizable continuum, "pure" functionals such as BLYP underestimate this overall barrier somewhat, and estimates of Delta A(double dagger) approximate to 16 and 17 kcal/mol are obtained at the B3LYP and CCSD(T) levels, respectively, in excellent agreement with the experiment. | |
dc.format.extent | 7 | |
dc.language.iso | eng | |
dc.relation.ispartof | Inorganic Chemistry | en |
dc.rights | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work see DOI: 10.1021/ic902508z | en |
dc.subject | Density-functional theory | en |
dc.subject | 1st-principles molecular-dynamics | en |
dc.subject | Polarizable continuum model | en |
dc.subject | Main-group thermochemistry | en |
dc.subject | Aqueous-solution | en |
dc.subject | Noncovalent interactions | en |
dc.subject | Free-energy | en |
dc.subject | Basis-sets | en |
dc.subject | AB-initio | en |
dc.subject | Complexes | en |
dc.subject | QD Chemistry | en |
dc.subject.lcc | QD | en |
dc.title | Oxygen exchange in uranyl hydroxide via two "nonclassical" ions | en |
dc.type | Journal article | en |
dc.description.version | Postprint | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.contributor.institution | University of St Andrews. EaSTCHEM | en |
dc.identifier.doi | https://doi.org/10.1021/ic902508z | |
dc.description.status | Peer reviewed | en |
dc.date.embargoedUntil | 2011-03-24 |
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