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dc.contributor.authorDavis, John C.
dc.contributor.authorBuehl, Michael
dc.contributor.authorKoch, Klaus R.
dc.date.accessioned2014-08-21T23:01:32Z
dc.date.available2014-08-21T23:01:32Z
dc.date.issued2013-08-22
dc.identifier.citationDavis , J C , Buehl , M & Koch , K R 2013 , ' Probing Isotope Shifts in 103 Rh and 195 Pt NMR Spectra with Density Functional Theory ' , Journal of Physical Chemistry A , vol. 117 , no. 33 , pp. 8054-8064 . https://doi.org/10.1021/jp405453cen
dc.identifier.issn1089-5639
dc.identifier.otherPURE: 105534704
dc.identifier.otherPURE UUID: 091a87be-4678-4f5f-8c4f-d33b3637370d
dc.identifier.otherWOS: 000323593700043
dc.identifier.otherScopus: 84883165860
dc.identifier.otherORCID: /0000-0002-1095-7143/work/48131764
dc.identifier.urihttp://hdl.handle.net/10023/5213
dc.description.abstractZero-point vibrationally averaged (rg0) structures were computed at the PBE0/SDD/6-31G* level for the [Pt35Cln37Cl5–n(H218O)]− (n = 0–5), cis-Pt35Cln37Cl4–n(H218O)(H216O) (n = 0–4), fac-[Pt35Cln37Cl3–n(H218O)(H216O)2]+ (n = 0–3), [Pt35Cln37Cl5–n(16/18OH)]2– (n = 0–5), cis-[Pt35Cln37Cl4–n(16/18OH)2]2– (n = 0–4), fac-[Pt35Cln37Cl3–n(16/18OH)3]2– (n = 0–3), cis-[Pt35Cln37Cl2–n(16/18OH)4]2– (n = 0–2), [Pt35Cln37Cl1–n(16/18OH)5]2– (n = 0–1), [Rh35Cln37Cl5–n(H2O)]2– (n = 0–5), cis-[Rh35Cln37Cl4–n(H2O)2]− (n = 0–4), and fac-Rh35Cln37Cl3–n(H2O)3 (n = 0–3) isotopologues and isotopomers. Magnetic shielding constants, computed at the ZORA-SO/PW91/QZ4P/TZ2P level, were used to evaluate the corresponding 35/37Cl isotope shifts on the 195Pt and 103Rh NMR spectra, which are known experimentally. While the observed effects are reproduced reasonably well computationally in terms of qualitative trends and the overall order of magnitude (ca. 1 ppm), quantitative agreement with experiment is not yet achieved. Only small changes in M–Cl and M–O bonds upon isotopic substitution, on the order of femtometers, are necessary to produce the observed isotope shifts.
dc.format.extent11
dc.language.isoeng
dc.relation.ispartofJournal of Physical Chemistry Aen
dc.rightsCopyright 2013, American Chemical Society. This document is the unedited author's version of a Submitted Work that was subsequently accepted for publication in The Journal of Physical Chemistry A after peer review. To access the final edited and published work, see http://pubs.acs.org/doi/abs/10.1021/jp405453cen
dc.subjectMolecular orbital methodsen
dc.subjectSpin coupling constantsen
dc.subjectAcidic aqueous solutionen
dc.subjectGaussian type basisen
dc.subjectChemical shfitsen
dc.subjectTemperature dependenceen
dc.subjectVibrational correctionsen
dc.subjectUnambiguous speciationen
dc.subjectOrganic moleculesen
dc.titleProbing Isotope Shifts in 103Rh and 195Pt NMR Spectra with Density Functional Theoryen
dc.typeJournal articleen
dc.description.versionPostprinten
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.identifier.doihttps://doi.org/10.1021/jp405453c
dc.description.statusPeer revieweden
dc.date.embargoedUntil2014-08-22


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