Thompson, J. A. and Vila-Nadal, L. (2024) Computation of 31P NMR chemical shifts in Keggin−based lacunary polyoxotungstates. Dalton Transactions, 53(2), pp. 564-571. (doi: 10.1039/D3DT02694A) (PMID:38054391)
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Abstract
Density Functional Theory (DFT) calculations were employed to systematically study the accuracy of various exchange-correlation functionals in reproducing experimental 31P NMR chemical shifts, δExp(31P) for Keggin, [PW12O40]3− and corresponding lacunary clusters: [PW11O39]7−, [A-PW9O34]9−, and [B-PW9O34]9−. Initially, computed chemical shifts, δCalc(31P) were obtained with without neutralising their charge in which associated error, δError(31P), decreased as a function of Hartree–Fock (HF) exchange, attributed to constriction of the P–O tetrahedron. By comparison, δCalc(31P) performed with explicitly located counterions to render the system charge neutral, reduced discrepancies, δError(31P) by 1–2 ppm. However, uncertainties in δCalc(31P) remain, particularly for [B-PW9O34]9− anions attributed to direct electrostatic interactions between the counterions and the central tetrahedron. Optimal results were achieved using the PBE/TZP//PBE0/TZP method, achieving a mean absolute error (MAE) and a mean squared error (MSE) of 4.03 ppm. Our results emphasize that understanding the nature of the electrolyte and solvent environment is essential to obtaining reasonable agreement between theoretical and experimental results.
| Item Type: | Articles |
|---|---|
| Additional Information: | Financial support for this work was provided by University of Glasgow and the Engineering and Physical Sciences Research Council Grants (EP/S030603/1; EP/V048341/1; EP/S031170/1), Royal Society of Chemistry RSC Hardship Grant (COVID-19). We thank the EPSRC Doctoral Training Partnership (DTP) funding received by the University of Glasgow for Jake A. Thompson PhD studentship ‘Exploring N2 fixation with metal oxides’ project 2442596 (EP/R513222/1; EP/T517896/1). |
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Vila-Nadal, Dr Laia and Thompson, Mr Jake |
| Authors: | Thompson, J. A., and Vila-Nadal, L. |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | Dalton Transactions |
| Publisher: | Royal Society of Chemistry |
| ISSN: | 1477-9226 |
| ISSN (Online): | 1477-9234 |
| Published Online: | 23 November 2023 |
| Copyright Holders: | Copyright © The Royal Society of Chemistry 2023 |
| First Published: | First published in Dalton Transactions 53(2):564-571 |
| Publisher Policy: | Reproduced under a Creative Commons license |
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