The accuracy limit of chemical shift predictions for species in aqueous solution

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dc.contributor.authorMaste, Stefan
dc.contributor.authorSharma, Bikramjit
dc.contributor.authorPongratz, Tim
dc.contributor.authorGrabe, Bastian
dc.contributor.authorHiller, Wolf
dc.contributor.authorErlach, Markus Beck
dc.contributor.authorKremer, Werner
dc.contributor.authorKalbitzer, Hans Robert
dc.contributor.authorMarx, Dominik
dc.contributor.authorKast, Stefan M.
dc.date.accessioned2025-09-09T12:38:57Z
dc.date.available2025-09-09T12:38:57Z
dc.date.issued2024-02-05
dc.description.abstractInterpreting NMR experiments benefits from first-principles predictions of chemical shifts. Reaching the accuracy limit of theory is relevant for unambiguous structural analysis and dissecting theoretical approximations. Since accurate chemical shift measurements are based on using internal reference compounds such as trimethylsilylpropanesulfonate (DSS), a detailed comparison of experimental with theoretical data requires simultaneous consideration of both target and reference species ensembles in the same solvent environment. Here we show that ab initio molecular dynamics simulations to generate liquid-state ensembles of target and reference compounds, including explicitly their short-range solvation environments and combined with quantum-mechanical solvation models, allows for predicting highly accurate 1H (∼0.1–0.5 ppm) and aliphatic 13C (∼1.5 ppm) chemical shifts for aqueous solutions of the model compounds trimethylamine N-oxide (TMAO) and N-methylacetamide (NMA), referenced to DSS without any system-specific adjustments. This encompasses the two peptide bond conformations of NMA identified by NMR. The results are used to derive a general-purpose guideline set for predictive NMR chemical shift calculations of NMA in the liquid state and to identify artifacts of force field models. Accurate predictions are only obtained if a sufficient number of explicit water molecules is included in the quantum-mechanical calculations, disproving a purely electrostatic model of the solvent effect on chemical shifts.en
dc.identifier.urihttp://hdl.handle.net/2003/43872
dc.language.isoen
dc.relation.ispartofseriesPhysical chemistry, chemical physics; 26(7)
dc.rights.urihttp://creativecommons.org/licenses/by/3.0/
dc.subject.ddc540
dc.titleThe accuracy limit of chemical shift predictions for species in aqueous solutionen
dc.typeText
dc.type.publicationtypeArticle
dcterms.accessRightsopen access
eldorado.doi.registerfalse
eldorado.secondarypublicationtrue
eldorado.secondarypublication.primarycitationMaste, S., Sharma, B., Pongratz, T., Grabe, B., Hiller, W., Erlach, M. B., Kremer, W., Kalbitzer, H. R., Marx, D., & Kast, S. M. (2024). The accuracy limit of chemical shift predictions for species in aqueous solution. Physical Chemistry, Chemical Physics, 26(7), 6386–6395. https://doi.org/10.1039/d3cp05471c
eldorado.secondarypublication.primaryidentifierhttps://doi.org/10.1039/D3CP05471C

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