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dc.contributor.authorEsteban-Gómez, David
dc.contributor.authorCassino, Claudio
dc.contributor.authorBotta, Mauro
dc.contributor.authorPlatas-Iglesias, Carlos
dc.date.accessioned2020-04-03T08:01:00Z
dc.date.available2020-04-03T08:01:00Z
dc.date.issued2014-01-06
dc.identifier.citation17O and 1H relaxometric and DFT study of hyperfine coupling constants in [Mn(H2O)6]2+. D. Esteban-Gómez, C. Cassino, M. Botta and C. Platas-Iglesias, RSC Adv., 2014, 7094–7103. DOI: 10.1039/C3RA45721D.es_ES
dc.identifier.issn2046-2069
dc.identifier.urihttp://hdl.handle.net/2183/25295
dc.description.abstract[Abstract] Nuclear Magnetic Relaxation Dispersion (NMRD) profiles and 17O NMR chemical shifts and transverse relaxation rates of aqueous solutions of [Mn(H2O)6]2+ were recorded to determine the parameters governing the relaxivity in this complex and the 17O and 1H hyperfine coupling constants (HFCCs). The analysis of the NMRD and 17O NMR data provided a water exchange rate of kex298 = 28.2 × 106 s−1, and AO/ħ and AH/ħ hyperfine coupling constants of −34.6 and 5.4 rad s−1, respectively. DFT calculations (TPSSh model) performed on the [Mn(H2O)6]2+ and [Mn(H2O)6]2+·12H2O systems were used to evaluate theoretically the 17O and 1H HFCCs responsible for the 17O NMR chemical shifts and the scalar contributions to 17O and 1H NMR relaxation rates. The use of a mixed cluster–continuum approach with the explicit inclusion of second-sphere water molecules is critical for an accurate calculation of HFCCs of coordinated water molecules. The impact of complex dynamics on the calculated HFCCs was evaluated with the use of molecular dynamics simulations within the atom-centered density matrix propagation (ADMP) approach. These molecular dynamics simulations show that the Aiso values are critically affected by the distance between the oxygen atom of the coordinated water molecule and the MnII ion, as well as by the orientation of the water molecule plane with respect to the Mn–O vector. The substantial scalar contribution to relaxivity observed for [Mn(H2O)6]2+ is related to a combination of a slow water exchange rate and a slow electron spin relaxation.es_ES
dc.description.sponsorshipXunta de Galicia; EM2012/088es_ES
dc.language.isoenges_ES
dc.publisherRoyal Society of Chemistryes_ES
dc.relation.urihttps://doi.org/10.1039/c3ra45721des_ES
dc.subjectRelaxivityes_ES
dc.subjectHiperfine coupling constantses_ES
dc.subjectSpin relaxationes_ES
dc.subjectMolecular dynamics simulationses_ES
dc.title17O and 1H relaxometric and DFT study of hyperfine coupling constants in [Mn(H2O)6]2+es_ES
dc.typeinfo:eu-repo/semantics/articlees_ES
dc.rights.accessinfo:eu-repo/semantics/openAccesses_ES
UDC.journalTitleRSC Advanceses_ES
UDC.volume4es_ES
UDC.issue14es_ES
UDC.startPage7094es_ES
UDC.endPage7103es_ES


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